CN103249777B

CN103249777B - The epoxy systems and amine polymer system and preparation method thereof that improve

Info

Publication number: CN103249777B
Application number: CN201180059453.6A
Authority: CN
Inventors: J·D·艾尔莫; L·S·科里; J·R·海特
Original assignee: Hexion Inc
Current assignee: West Lake Epoxy Resin Co; West Lake Olefin Co ltd
Priority date: 2010-12-13
Filing date: 2011-11-28
Publication date: 2016-01-20
Anticipated expiration: 2031-11-28
Also published as: KR101457832B1; CN105482077B; ES2776995T3; BR112013014588B1; WO2012082341A1; US8586704B2; KR20130114195A; BR112013014588A8; CA2820462A1; CN105482077A; BR112013014588A2; TWI486376B; DK2652040T3; EP2652040A4; US9234077B2; EP2652040B1; TW201229090A; US20120149804A1; US20140046001A1; EP2652040A1

Abstract

The invention provides a kind of composition for the formation of tensio-active agent, aqueous dispersion and solidifying agent and method.On the one hand, the present invention relates to the epoxy-functional tensio-active agent of the improvement prepared by the reaction of epoxy composite and amide amine composition, this amide amine composition is formed by the blend of the polyoxyalkylene polyol of acid blocked.The epoxy-functional tensio-active agent of this improvement can react to obtain aqueous dispersion with excessive epoxy composite and water.This amide amine composition can be the reaction mixture of the polyoxyalkylene composition of diamine compound and acid blocked, and this polyoxyalkylene composition is by two or more polyoxyalkylene polyol compound formation.Epoxy-functional tensio-active agent can react to form the compound being suitable as solidifying agent with amine compound.

Description

The epoxy systems and amine polymer system and preparation method thereof that improve

Invention field

The present invention relates to tensio-active agent and the aqueous dispersion of epoxy resin.On the one hand, the present invention relates to the amine-functionalized tensio-active agent of improvement, and the epoxy-functional tensio-active agent of improvement prepared by the reaction of the amine composition related to by being formed by polyoxyalkylene polyol and epoxy composite.

Background of invention

The aqueous dispersion of epoxy resin is all known for many years.But these dispersions are considered to as the performance of coating composition the resemblance containing solvent being not so good as them.Poly-(propylene oxide) poly-(oxyethane) ethanol becoming known for the emulsible tensio-active agent of epoxy component such as nonyl phenol ethoxylate, poly-(oxyethane) ethanol of alkylphenol initiation, alkylphenol are caused easily moves to surface interface with the segmented copolymers comprising poly-(propylene oxide) interior block and two kinds of outer blocks of poly-(oxyethane) ethanol, by inference, they have adverse influence to film properties there.

In addition, because epoxy resin aqueous dispersion is more widely used in the industry, therefore need to improve handling property, such as stability in storage.Due to the existence of amine nitrogen atom in surfactant molecule, the stability in storage of many moisture epoxy dispersion declines in time.Along with the pH value of moisture dispersion increases to above 9.8, this stability in storage no longer to measure over year, but to measure over the moon.

It is also contemplated that reduce the particle size of solid, or the amount of the tensio-active agent needed under reducing given solid level, or expect to use less tensio-active agent dispersible solid under given particle size.Usually, need a large amount of tensio-active agents to reduce particle size and solid effectively in disperse water, this causes increasing pH value and reduces stability in storage.Reduce surfactant level causes particle size increase with control ph.

Therefore, needs are also existed to the tensio-active agent forming the aqueous dispersion for the formation of epoxy resin improved.

Summary of the invention

Embodiment of the present invention relate to for epoxy resin aqueous dispersion with for the tensio-active agent in amine polymer composition.This tensio-active agent can be used as the solidifying agent in epoxy composite by functionalization and modification further.On the one hand, the present invention relates to the epoxy-functional tensio-active agent that the amide amine composition formed by the blend of the polyoxyalkylene polyol by acid blocked and epoxy composite react the improvement prepared.

An aspect of of the present present invention provides a kind of amide amine composition, it comprises the polyoxyalkylene composition of the acid blocked of the polyoxyalkylene polyol compound of two or more acid blocked and the reaction product of diamine compound, wherein the polyoxyalkylene composition of acid blocked there are 1.1 or more much higher dispersivenesses and the polyoxyalkylene polyol compound of two or more acid blocked described have about 50% to about 100% from hydroxyl end groups oxidation carboxylic end group, and diamine compound comprises the second amine substituting group of the substituent first amine substituting group of primary amine and primary amine substituting group or Secondary amine substituents, wherein reaction product comprises the amide amine compound with following formula:

Wherein R ₁and R ₂in each comprise hydrogen atom or be selected from the substituting group of group of the branching with 1 to 21 carbon atoms or linear aliphatic, alicyclic, aromatic substituents and their combination and its subset, and R ₁and R ₂in at least one comprise hydrogen atom, R ₃it is divalence hydrocarbon substituent, it is selected from the group of the branching with 2 to 18 carbon atoms or linear aliphatic, alicyclic, aromatic substituents and their combination and its subset, n is the mean number of about 18 to about 500, X is hydrogen atom or the substituting group being selected from the group be made up of methyl substituents, ethyl substituent, hydroxymethyl substituents and their combination, and Y is hydrogen atom or the substituting group of group being selected from methyl substituents, ethyl substituent, hydroxymethyl substituents and their combination.

Another aspect provides a kind of method for the formation of amide amine composition, it comprises the polyoxyalkylene composition of the acid blocked of the polyoxyalkylene polyol compound providing two or more acid blocked, wherein the polyoxyalkylene composition of acid blocked there are 1.1 or more much higher dispersivenesses and the polyoxyalkylene polyol compound of two or more acid blocked described have about 50% to about 100% from hydroxyl end groups oxidation carboxylic end group, diamine compound is provided, it comprises the second amine substituting group of the substituent first amine substituting group of primary amine and primary amine substituting group or Secondary amine substituents, and the polyoxyalkylene composition of acid blocked and the diamine compound of first are reacted with forming reactions product, wherein reaction product comprises the amide amine compound with following formula:

Another aspect of the present invention, provides a kind of epoxy composite, and it comprises the reaction product prepared by epoxy component and amide amine composition react, and wherein this reaction product comprises the epoxy-functional tensio-active agent with following structure:

And m is 1 to 11, n is 1 to 3, q is 0 to 8, p is about 18 to about 500, X is hydrogen atom, methyl substituents, ethyl substituent, hydroxymethyl substituents, their subset or their combination, each Y is hydrogen atom, methyl substituents, ethyl substituent, hydroxymethyl substituents, their subset or their combination, and R ₁₇can be alkyl group, aromatic yl group, carboxyl groups and their combination of their subset sums.

Summary of drawings

When considering to combine with accompanying drawing, the advantage of the disclosure of invention and other side, owing to becoming better understood equally by reference to following detailed description, and be easy to for a person skilled in the art understand, wherein run through several figures of accompanying drawing, same reference symbol marks same or analogous unit, and wherein:

Fig. 1 illustrates that the epoxy dispersion of the materials and methods formation using the present invention to describe is compared with the epoxy dispersion of prior art, the chart of epoxy dispersion particle size stability at 25 DEG C.

Detailed Description Of The Invention

Embodiment of the present invention relate to for the aqueous dispersion of epoxy resin and the tensio-active agent for amine polymer composition.This tensio-active agent can be used as the solidifying agent in epoxy composite by functionalization and modification further.On the one hand, the present invention relates to the epoxy-functional tensio-active agent that the amide amine formed by the blend of the polyoxyalkylene polyol by acid blocked and composition epoxy composite react the improvement prepared.

The blend that embodiments more of the present invention relate to by comprising two or more compounds with the polyoxyalkylene polyol of the acid blocked of different molecular weight (being also known as the polyoxyalkylene polyol of oxidation and carboxylated polyoxyalkylene) forms tensio-active agent.A kind of tensio-active agent can be the functionalized polyoxyalkylene original surface promoting agent of the daiamid prepared by the compound blend of the polyoxyalkylene polyol comprising acid blocked.Can react the tensio-active agent forming epoxy-functional after the polyoxyalkylene surfactants that this daiamid is functionalized further, it can be formed separately or original position is formed together with epoxy resin.The tensio-active agent of epoxy-functional may be used for forming water-base epoxy dispersion.The tensio-active agent of epoxy-functional can also react with the tensio-active agent forming amine end-blocking further, and the tensio-active agent of this amine end-blocking may be used for water-based amine polymer dispersion, or as being used for the solidifying agent of epoxy composite.The dispersion that thermosetting coating and fiber size preparation can be described by the present invention.

Wondrous and blend that the is polyoxyalkylene polyol of the different molecular weight of unexpected discovery partial oxidation provides unforeseeable hyperergy tensio-active agent, its for by epoxy-functional with amine-functionalized polymer emulsified become " water bag resin " dispersion.This super performance observed comprises the particle size of reduction and the storage life of improvement, and improves the Non-volatile content of (higher) and the epoxy polymer dispersion of improvement (lower) viscosity.

An aspect of of the present present invention, the reaction product that the amide amine composition of the original surface promoting agent that the present invention describes has the composition and diamine compound that comprise the polyoxyalkylene polyol of acid blocked of the polyoxyalkylene polyol compound of the acid blocked of the associating polymolecularity of 1.1 or higher by two or more is formed, this polyoxyalkylene polyol compound is oxidized to and makes hydroxyl be about 50% to about 100% to the transformation efficiency of carboxyl, and diamine compound comprises the second substituting group of the substituent first amine substituting group of primary amine and primary amine substituting group or Secondary amine substituents.

the manufacture of amide amine compound and composition

On the one hand, the amide amine compound that the method that described by the present invention is formed, the functionalized polyoxyalkylene original surface promoting agent (being also called amide amine original surface promoting agent in the present invention) of such as daiamid has following formula:

R ₁for hydrogen atom or the substituting group of group being selected from the branching with 1 to 21 carbon atoms or linear aliphatic, alicyclic, aromatic substituents and their combination and its subset.R ₂for hydrogen atom or the substituting group of group being selected from the branching with 1 to 21 carbon atoms or linear aliphatic, alicyclic, aromatic substituents and their combination and its subset, and R ₁and R ₂in at least one comprise hydrogen atom, R ₃be divalence hydrocarbon substituent, it is selected from the group of the branching with 2 to 18 carbon atoms or linear aliphatic, alicyclic, aromatic substituents and their combination and its subset, and m can be 1,2 or 3, and n can be the mean number of about 18 to about 500.For repeating unit, x can be hydrogen atom or the substituting group being selected from the group be made up of methyl substituents, ethyl substituent, hydroxymethyl substituents and their combination.Y can be hydrogen atom or the substituting group of group being selected from methyl substituents, ethyl substituent, hydroxymethyl substituents and their combination.Oxyalkylene can be random or block polymerization.

The functionalized polyoxyalkylene original surface promoting agent of the daiamid of formula (I) can have the amine value of about 8 to about 30, and such as about 12 to about 24, such as about 14 to about 18.The functionalized polyoxyalkylene original surface promoting agent of this daiamid can be hydrophilic.

The functionalized polyoxyalkylene original surface promoting agent of the daiamid of formula (I) can have the weight-average molecular weight (M of about 200 to about 22000 _w), such as about 2000 to about 12000, such as about 4000 to about 10000.Number-average molecular weight (M _n) can be about 180 to about 20000, such as about 1800 to about 11000, such as about 3000 to about 8000.Number all (nominal) molecular weight represents that the gross weight of polymkeric substance is divided by the molecule sum in gross weight.

In addition, molecular weight distribution can be expressed as the relevant Z-average molecular weight (M that those skilled in the art relevant to molecular weight distribution analysis understand usually further _z) and (Z+1)-average molecular weight (M _z+1).Z-average molecular weight (M _z) can be about 300 to about 30000, such as about 3000 to about 20000, such as about 5000 to about 14000.(Z+1)-average molecular weight (M _z+1) can be about 400 to about 40000, such as about 4000 to 27000, such as about 6500 to about 19000.

On the one hand, the diamine reactant that the compound (being also known as the polyoxyalkylene polyol of oxidation and carboxylated polyoxyalkylene) comprising the polyoxyalkylene polyol of acid blocked that the polyoxyalkylene original surface promoting agent that multiamide is amine-functionalized can have a different molecular weight by two or more and at least one the present invention describe is formed.

Described at least one diamine compound can comprise the second amine substituting group of the substituent first amine substituting group of primary amine and primary amine substituting group or Secondary amine substituents.This reaction can be carried out with excessive or inexcessive diamines, comprises the amine of about 12:1 to about 2:3 and the equivalence ratio of acid.

Optionally, the polyoxyalkylene original surface promoting agent that multiamide is amine-functionalized can be formed by the compound of polyoxyalkylene polyol and at least one diamines comprising acid blocked.Described at least one diamine compound can comprise the second amine substituting group of the substituent first amine substituting group of primary amine and Secondary amine substituents.This reaction can use excessive diamines to carry out, and comprises the amine of about 3:1 to about 1:2 and acid equivalent ratio.

In the embodiment of an original surface promoting agent, the amine-functionalized polyoxyalkylene original surface promoting agent of multiamide can by the present invention describe there is different molecular weight two or more comprise the blend of the compound of the polyoxyalkylene polyol of acid blocked and at least one diamine reactant is formed.Such as, comprise the compound of the polyoxyalkylene polyol of the first acid blocked and there is the blend comprising the compound of the polyoxyalkylene polyol of the second acid blocked, these compounds and at least one diamine reactant of the compound molecular weight more high molecular than the polyoxyalkylene polyol comprising the first acid blocked.This reaction can use the amine of about 12:1 to about 1:2 to carry out with the equivalence ratio of acid.

On the other hand, the polyoxyalkylene original surface promoting agent that multiamide is amine-functionalized can be formed amide amine separately by the compound comprising the polyoxyalkylene polyol of acid blocked by two or more and afterwards reaction product is merged into the blend of the amine-functionalized polyoxyalkylene original surface promoting agent of multiamide and formed.At least one diamines that each reaction can describe with the present invention carries out and each reaction can use identical or different diamines.The method that each reaction can use the present invention to describe is carried out and the amine of about 12:1 to about 1:2 can be used to carry out with the equivalence ratio of acid.

Enforcement side's amine of original surface surfactant composition comprises and forms amide amine mixture by two kinds of compound blends together comprising the polyoxyalkylene polyol of acid blocked, the blending ratio of the polyoxyalkylene polyol of the polyoxyalkylene polyol of the acid blocked of the first molecular weight and the acid blocked of the second molecular weight be about 3:17 to about 17:3, the blending ratio of such as about 11:9.Optionally, this blend can have about 15wt.% to about 85wt.%, the polyoxyalkylene polyol of the acid blocked of first molecular weight of such as about 45%, and there is about 85wt.% to about 15wt.%, the polyoxyalkylene polyol of the acid blocked of second molecular weight of such as about 55%.Second compound comprising the polyoxyalkylene polyol of acid blocked has the higher molecular weight of the molecular weight that comprises the compound of the polyoxyalkylene polyol of acid blocked than first.The polyoxyalkylene polyol of the acid blocked of the first molecular weight can have the weight-average molecular weight of as described below about 200 to about 5000, such as about 2000 to about 5000, and the polyoxyalkylene polyol of the acid blocked of the second molecular weight can have the as described below weight-average molecular weight being greater than 4000 to about 16000.

The compound comprising the polyoxyalkylene polyol of acid blocked can have following formula:

R ₃can be hydrogen atom or the divalence hydrocarbon substituent of group being selected from branching or linear aliphatic, alicyclic, aromatic substituents and their combination and its subset with 2 to 18 carbon atoms, and this hydrocarbon substituent have hydroxyl end groups or carboxyl end groups.For repeating unit, m can be 1-11, and can be the mean number of about 18 to about 500 for n the compound that each comprises the polyoxyalkylene polyol of acid blocked accordingly.X can be hydrogen atom, methyl substituents, ethyl substituent or hydroxymethyl substituents.Y can be hydrogen atom, methyl substituents, ethyl substituent or hydroxymethyl substituents.The compound comprising the polyoxyalkylene polyol of acid blocked can be random or block polymer.The compound comprising polyoxyalkylene polyol can have the hydroxyl end groups that about 50% arrives the substituting group (carboxylic end group/carboxyl end groups) of about oxidized formation acid blocked of 100%, such as about 70% to about 95%.

Formula (IIa) comprises the weight-average molecular weight (M of the compound of the polyoxyalkylene polyol of acid blocked _w) can be about 200 to about 22000, such as about 2000 to about 10000, such as about 4000 to about 10000.Its number-average molecular weight (M _n) can be about 180 to about 20000, such as about 1800 to about 11000, such as about 3000 to about 8000.This number all (nominal) molecular weight represents the total mole number of the gross weight of polymkeric substance divided by the molecule comprised in polymkeric substance.

Two or more are comprised to the merging composition of the compound of the polyoxyalkylene polyol of acid blocked, said composition can have the polymolecularity being greater than about 1.1.On the one hand, this composition can have the polymolecularity of about 1.15 to about 5, and such as about 1.22 to about 1.70.This polymolecularity is by weight-average molecular weight (M _w) divided by number-average molecular weight (M _n) calculate.

The suitable example comprising the compound of the polyoxyalkylene polyol of acid blocked comprises the polyoxyethylene glycol of acid blocked, the polypropylene glycol of acid blocked and their combination.Such as, two or more each comprising in the compound of the polyoxyethylene glycol of acid blocked can have following molecular formula:

For each corresponding polyoxyalkylene diols compound, N can be the mean number of about 18 to about 500.For repeating unit, m can be 1-11 and each be comprised accordingly to the compound of the polyoxyethylene glycol of acid blocked, and n can be the mean number of about 18 to about 500.X can be hydrogen atom, methyl substituents, ethyl substituent or hydroxymethyl substituents.Y can be hydrogen atom, methyl substituents, ethyl substituent or hydroxymethyl substituents.The compound comprising the polyoxyethylene glycol of acid blocked can be random or block polymer.This compound comprising polyoxyethylene glycol can have the hydroxyl end groups of about oxidized formation carboxylic end group of 50% to 100%, such as about 70% to about 95%.

The weight-average molecular weight comprising the compound of the polyoxyethylene glycol of acid blocked of formula (IIb) can be about 200 to about 22000, such as about 2000 to about 10000, such as about 4000 to about 10000.Described number-average molecular weight (M _n) can be about 180 to about 20000, such as about 1800 to about 11000, such as about 3000 to about 8000.This number all (nominal) molecular weight represents the total mole number of the gross weight of polymkeric substance divided by the molecule comprised in polymkeric substance.

In one embodiment, the composition comprising the compound of the polyoxyalkylene diols of acid blocked can be formed by the mixture of two or more polyoxyalkylene polyol compounds of oxidation, such as two or more polyoxyalkylene diols compounds.Optionally, the composition comprising the compound of the polyoxyalkylene diols of acid blocked can be formed by being oxidized each in two or more polyoxyalkylene polyol compounds separately, such as two or more polyoxyalkylene diols compounds, and the compound of the polyoxyalkylene polyol comprising acid blocked is accordingly merged into a kind of composition.

For being oxidized separately and merging afterwards or co-oxidation, the blending ratio of two kinds of polyoxyalkylene polyol compounds can be the polyoxyalkylene polyol of first molecular weight of about 3:17 to about 17:3 and the polyoxyalkylene polyol of the second molecular weight, the such as blending ratio of about 4:1 to about 1:4, such as about 11:9.Optionally, this blending ratio is represented by weight percentage, can be about 15wt.% to about 85wt.%, such as about 45% the polyoxyalkylene polyol of the first molecular weight, and approximately 85wt.% to about 15wt.%, such as about 55% the polyolefin polyhydric alcohol of the second molecular weight.Second polyoxyalkylene polyol has the molecular weight of the molecular weight higher than the first polyoxyalkylene polyol.

Polyoxyalkylene polyol compound can be oxidized by the oxidation of polyoxyalkylene polyol or carboxylated/acidifying comprises the compound of the polyoxyalkylene polyol of acid blocked with formation, it includes but not limited to the U.S. patent No. 6,235, the method described in 931, by reference to the aspect of itself and application claims and specification sheets and reconcilable degree and be incorporated to the present invention.

In the embodiment of a formation method, free radical (such as 2 is there is in water, 2,6,6-tetramethyl--1-piperidines oxygen) and mineral acid (such as nitric acid) when oxygen-containing gas is joined in polyoxyalkylene polyol oh group is oxidized to hydroxy-acid group.If desirably the polyolefin polyhydric alcohol of two acid blocked, substantially all alcohol groups are all oxidized to hydroxy-acid group.The compound comprising the polyolefin polyhydric alcohol of acid blocked can also by Williamson ether synthesis preparation, and wherein polyoxyalkylene polyol and Mono Chloro Acetic Acid and/or ester react in the presence of base.

In the embodiment of a reaction conditions, temperature can be about 20 DEG C to about 70 DEG C, and pressure is pressed onto in the scope of the highest about 100psig at about air.After reaction, from reactor, distill out remaining mineral acid and water.

In one embodiment, two kinds of compounds comprising the polyoxyalkylene polyol of acid blocked can be formed by the mixture of the polyoxyalkylene polyol compound of oxidation first molecular weight and the second molecular weight, such as there is the polyoxyethylene glycol of different molecular weight, blending ratio is the polyoxyalkylene polyol of first molecular weight of about 3:17 to about 17:3 and the polyoxyalkylene polyol of the second molecular weight, such as the blending ratio of about 11:9.The polyoxyalkylene polyol of the first molecular weight can have the molecular weight of about 200 to about 5000, and the second molecular weight polyoxyethylene alkene polyvalent alcohol can have the molecular weight being greater than 4000 to about 16000.Second molecular weight polyoxyethylene alkene polyvalent alcohol has the molecular weight higher than the polyoxyalkylene polyol of the first molecular weight.

The polyoxyalkylene polyol that the present invention describes comprises and is not limited by the polyoxyalkylene polyol of basic metal and DMC catalysts polymerization.This polyoxyalkylene polyol with water from causing, can cause with any glycol, including but not limited to liquid diol or glycerine, causing with bis-phenol, or causing with other active hydrogen organic compound comprising primary amine or secondary amine.

Suitable polyolefin polyhydric alcohol compound can have following formula:

R ₃can be hydrogen atom or the divalence hydrocarbon substituent of group being selected from branching or linear aliphatic, alicyclic, aromatic substituents and their combination and its subset with 2 to 18 carbon atoms, and each in this hydrocarbon substituent have hydroxyl end groups.For repeating unit, m can be 1-11 and for n each polyoxyalkylene polyol compound can be about 18 to about 500 mean number.X can be its combination of hydrogen atom, methyl substituents, ethyl substituent, hydroxymethyl substituents, hydroxyl end groups and their subset sums.Y can be its combination of hydrogen atom, methyl substituents, ethyl substituent, hydroxymethyl substituents, hydroxyl end groups and their subset sums.Suitable polyoxyalkylene polyol comprises polyoxyethylene glycol (polyethers) (PEG), polypropylene polyether glycol, 1,2 polybutene polyether glycols, Isosorbide-5-Nitrae polybutene polyether glycol and their combination.Each polyoxyalkylene diols can comprise the monoalky lether (" polyoxyalkylene diols ") of the segmented copolymer of polyoxyethylene glycol monoalky lether or oxyethane and propylene oxide or butylene oxide ring, or the segmented copolymer of oxyethane and propylene oxide or polybutylene oxide (" polyoxyalkylene diols ").

The example of suitable polyoxyethylene glycol (PEG) compound can have following formula:

For repeating unit, m can be 1-11 and for higher molecular weight compound n can be about 18 to about 500 mean number, such as about 230, and n for lower molecular weight compound can be 5 to 150, such as about 91.X can be hydrogen atom, methyl substituents, ethyl substituent, hydroxymethyl substituents, hydroxyl end groups and their combination of their subset sums.Y can be hydrogen atom, methyl substituents, ethyl substituent, hydroxymethyl substituents, hydroxyl end groups and their combination of their subset sums.

For repeating unit, m can be 1 to 11, and for higher molecular weight compound n can be 18 to 500, such as about 230, for lower molecular weight compound n can be 5 to 150, such as about 91.

No matter be form that is independent or combination, the number-average molecular weight (M of polyoxyalkylene diols compound _n) can be about 180 to about 20000, such as about 1800 to about 11000, such as about 3000 to about 8000.Number all (nominal) molecular weight represents that the gross weight of polymkeric substance is divided by the molecule sum comprised in polymkeric substance.No matter be form that is independent or combination, the weight-average molecular weight (M of polyoxyalkylene diols compound _w) can be about 200 to about 22000, such as about 2000 to about 10000, such as about 4000 to about 10000.

For the combination composition of two or more polyoxyalkylene polyols, said composition can have the polymolecularity of about 1.1, and such as 1.15 to 1.70 or 1.25 to about 1.55, such as 1.35 to about 1.45, it is by weight-average molecular weight (M _w) divided by number-average molecular weight (M _n) calculate.

In an example, first molecular weight polyoxyethylene alkene polyol compound can have the n value in 5 to 150 scopes, such as 45 to 115, such as about 91, condition is the first number-average molecular weight is about 2000 to about 5000, such as about 4000 and the first weight-average molecular weight is about 2200 to about 5500, such as about 4400.Second molecular weight polyoxyethylene alkene polyol compound can have the n value in about 18 to about 500 scopes, such as about 90 to about 365, such as about 230, condition is the second number-average molecular weight is about 4000 to about 18000, such as about 4000 to about 16000, such as about 8000 and the second weight-average molecular weight is about 4400 to about 17600, such as about 8800.In an example, the polyoxyalkylene polyol compound of corresponding first weight-average molecular weight and the second weight-average molecular weight can with the mixed in molar ratio of about 45:55.In blend, the mean value of n can be about 100 to about 205, and such as n can be about 150.

Polyoxyalkylene polyol comprises the compound distribution with variable number ethylene oxide unit and/or other oxyalkylene averaging units usually, and the number of unit quoted is the whole real number closest to statistics mean value and distribution peaks.The whole real number used in the present invention refers to the numeral of positive integer or integer fraction.

Comprise the compound of the polyoxyalkylene polyol of acid blocked, no matter be form that is independent or combination, can react with at least one polyamine compounds after it, such as at least one diamine compound, with the polyethylene oxide original surface promoting agent that the multiamide forming the present invention's description is amine-functionalized.

This reaction is carried out in reaction vessel under the condition of condensation.Suitable reaction conditions comprises the temperature be heated to by starting raw material at atmosheric pressure within the scope of about 100 DEG C to about 250 DEG C, and distills condensation by-product, water.Together with water, excessive polyamine compounds also can by distillation removing.In order to improve the removal of water and any excessive polyamine compounds further, can use the container pressure of vacuum or reduction after initiation reaction, such as about 10 to about 200mmHg (holder).

In an embodiment of described diamine compound, each amido of diamine compound is primary amine, and diamine compound has following formula:

H ₂N-R ₃-NH ₂(IV).

R ₃be divalence hydrocarbon substituent, it is selected from the group of the branching with 2 to 18 carbon atoms or linear aliphatic, alicyclic, aromatic substituents and their combination and its subset.This divalence hydrocarbon substituent optionally can comprise one or more non-reacted oxygen and/or nitrogen-atoms in its main chain.At R ₃the nitrogen-atoms of 4 secondary nitrogen and/or tertiary N atom on average can be there is at most in each structure in group.At R ₃in group, Sauerstoffatom with average maximum 4 atoms or less can exist.Therefore, formula (IV) comprises two secondary amine compounds, and it comprises HR ₂n-R ₃-NHR ₂molecular formula, and R ₂it is the group being selected from the branching with 1 to 21 carbon atoms or linear aliphatic, alicyclic, aromatic substituents and their combination and its subset.

The example of suitable diamines such as comprises m-xylylene amine, 1,3-bis-(amino methyl) hexanaphthene, 2-methyl isophthalic acid, 5-pentane diamine, 1,3-pentane diamine, quadrol, diethylenetriamine, Triethylenetetramine (TETA), Polypropylene oxide diamine, 2,2 (4), 4-trimethylammonium 1,6-hexane diamine, isophorone diamine, 2,4 (6)-tolylene diamines, 1,6-hexane diamine, 1,2-diamino-cyclohexane, to diamino-dicyclohexyl methane (PACM) and their combination.Suitable oxygen containing amine such as comprises 1，10-diamino-4，7-dioxadecane, 1,8-diamino-3,6-dioxaoctane, 1,13-diamino-4,7,10-trioxatridecane and their combination.

Can add according to the amount of compound molar excess relative to the polyoxyalkylene polyol comprising acid blocked according to the amine of formula (IV).This excessive diamine compound can be that about 6:1 adds to about 2:1 according to the mol ratio with carboxylic acid functional, and such as approximately 5:1 is to about 3:1, and such as about 4:1 is to about 3.2:1.When using excessive diamine compound, after reacting, unreacted diamine compound can be removed.

In addition, mono-epoxy compounds can be introduced with diamines simultaneously or in succession introduce to form the amine-functionalized polyoxyalkylene original surface promoting agent of multiamide further.This mono-epoxy compounds can be the mono-epoxy compounds that the present invention describes, and such as comprises C ₁₀the glycidyl ester of tertiary carboxylic acid.This mono-epoxy compounds can add according to certain amount, and the amount that this amount is enough to control diepoxy hydrophobic materials in follow-up diepoxy component is added is about 5% to about 40% hydrophobic materials, to form epoxy-capped tensio-active agent and/or epoxy dispersion.

Temperature of reaction between amide amine composition and the optional mono-epoxy compounds added does not limit.Suitable temperature of reaction in the scope of about 60 DEG C to about 150 DEG C and under the container pressure of vacuum or reduction, such as approximately 1KPa to about 30KPa.

Suitable mono-epoxy compounds comprises:

Wherein R ₄and R ₆identical or different and be that what to have 2 to 100 carbon atoms is optionally the alkenyl group of branching, or branching or linear alkyl, cycloalkyl, polyoxy alkyl; And R ₅hydrogen atom or the branching with 1-18 carbon atom or nonbranched alkyl.More than the R of a type ₅group is connected on aromatic nucleus.R ₁₅divalent alkyl or the aryl substituent with 3 to 20 carbon atoms.

This classification comprises the oxyethane (oxirane) of alkene, comprises oxybutylene, cyclohexene oxide, Styrene oxide 98min.; The glycidyl ether of monovalent alcohol, monovalent alcohol is methyl alcohol, ethanol, butanols, 2-Ethylhexyl Alcohol and dodecanol such as; Have the alcohol of at least 8 carbon atoms by succession oxyalkylene being added to the glycidyl ether of the oxyalkylene addition compound in corresponding alkanol (ROH), such as commodity are called those; The glycidyl ether of unit price phenol, such as phenol, methylphenol and in ortho position-or contraposition-use C ₁-C ₂₁other phenol that branching or nonbranched alkyl, aralkyl, alkaryl or alkoxyl group replace, such as nonyl phenol; The glycidyl ester of monocarboxylic acid, such as U.S.Pat.No.3,178, the sad glycidyl ester described in 500, the glycidyl ester of capric acid, lauric glycidyl ester, stearic glycidyl ester, the glycidyl ester of the glycidyl ester of eicosanoic acid and α, α-dialkyl group monocarboxylic acid, the document is thus by reference to being incorporated to the present invention; The glycidyl ester of unsaturated alcohol or unsaturated carboxylic acid, the glycidyl ester of such as neodecanoic acid; Epoxyoleic acid methyl esters, the positive butyl ester of epoxyoleic acid, epoxidation Uniphat A60, epoxidation ethyl linoleate and similar substance; The acetal of glycidyl allyl ether and glycidaldehyde.

The specific examples of single glycidyl end-capping reagent comprises alkyl glycidyl ether alkyl chain with 1-18 Linear carbon atom, such as butylglycidyl ether or C ₈-C ₁₄the mixing glycidyl ether of alkyl, toluene glycidyl ether, phenyl glycidyl ether, nonyl phenyl glycidyl glyceryl ether, to tert-butyl-phenyl glycidyl ether, 2-hexyl glycidyl ether, the glycidyl ether of neodecanoic acid and their combination.The example of other suitable monoepoxides comprises the epoxide that glycidated list is sour and formed by alpha-olefin and Racemic glycidol oxyalkyl organoalkoxysilane.

The example of the preferred monoepoxy resin be purchased such as comprises and to be allly obtained commercially by MomentiveSpecialtyChemicalsofColumbusOhio modifiers62,63,64,65 and 116 and resinE-10.

Fatty group mono-epoxy compounds is normally feature with hydrophobic, and it tends to improve the coalescent character of the curable epoxide agent composition that wherein mono-epoxy compounds uses at low temperatures, and tends to the second-order transition temperature reducing film or coating.Lower second-order transition temperature improves the shock strength of cured film.Aromatic series base list glycidyl mono-epoxy compounds can have the advantage making cured film have more resistance to stress under rigidity, chemical resistant properties and high temperature.Can use in the mono-epoxy compounds of these types any one, and use the advantage of their combination to be to obtain solvability, cohesiveness, physical strength and chemical-resistant whole machine balancing in the final product.

Optionally, in another embodiment of diamines, an amido is primary amine, and another amido is secondary amine, and it can have following formula:

R ₁-HN-R ₃-NH ₂(V)。

R ₃it is divalence hydrocarbon substituent, it is selected from the group of the branching with 2 to 18 carbon atoms or linear aliphatic, alicyclic, aromatic substituents and their combination and its subset, and optionally in its main chain, comprises one and multiple non-reacted Sauerstoffatom and/or nitrogen-atoms.R ₁be branching and linear aliphatic, the alicyclic or aromatic series divalent group with 1 to 21 carbon atoms, and optionally in its main chain, comprise one or more non-reacted oxygen or nitrogen-atoms.R ₁and R ₃in each can have the end group substituting group of group being selected from alkyl group (i.e. methyl group), oh group, alkylthio radicals and their combination and their subset further.Optionally, R ₁and R ₃total ring can be formed.

Optionally, formula (V) can be modified to have the 2nd R on the second nitrogen-atoms ₁group.Therefore, formula (V) can comprise formula HR ₁n-R ₃-NHR ₁two secondary amine compounds, and R ₁it is the substituting group of group being selected from the branching with 1 to 21 carbon atoms or linear aliphatic, alicyclic, aromatic substituents and their combination and their subset.

The suitable example comprising the diamines of a primary amine group and a secondary amine group such as comprises N-methyl ethylenediamine, N-butyl-1, 6-hexane diamine, N-cyclohexyl-1, 3-propanediamine, N-(2-amino-ethyl) piperazine, amino ethyl ethanolamine, N-methyl isophthalic acid, 4-cyclohexane diamine, N-oleyl-1, 3-propanediamine, N-Cocoalkyl-1, 3-propanediamine, N-(methylthio group) ethyl-1, 3-propanediamine, N-(line style or branching decyl) oxygen propyl group-1, 3-propanediamine, N-(line style or branching tridecyl) oxygen propyl group-1, 3-propanediamine, N-Cocoalkyl oxygen propyl group-1, 3-propanediamine, N-(octyl group/decyl) oxygen propyl group-1, 3-propanediamine and their combination.

Amine according to formula (V) can be that about 2:1 adds to about 1:2 according to the equivalent of carboxylic acid functional and the ratio of the mole number of amine, and such as approximately 3:2 is to about 2:3, and such as about 3:2 is to about 1:1.So, secondary in some embodiments, can add according to the amount of the not molar excess of two or more compounds comprising the polyoxyalkylene polyol of acid blocked relatively according to the amine of formula (V).Preferably, time different or backward with the reaction of the amine compound of formula (V) in add monoepoxide.Any excessive amine substance can be removed after amine reaction and/or monoepoxide reaction.

Optionally, amine according to formula (V) can be that about 2:1 is to about 1:2 according to the equivalent of carboxylic acid functional and the ratio of the mole number of amine, such as approximately 3:2 is to about 2:3, and such as about 3:2 to about 1:1 adds to and has one or more and comprise in the composition of the compound of the polyoxyalkylene polyol of acid blocked.In this alternate embodiment, monoepoxide can with the amine compound of formula (V) simultaneously or add to after which in reaction.Any excessive amine substance can be removed after amine reaction and/or monoepoxide reaction.

On the one hand, the present invention relates to the epoxy-functional tensio-active agent of the improvement for epoxy resin aqueous dispersion.Once manufacture amide amine composition, this epoxy-functional tensio-active agent has been prepared in the reaction just having a diepoxy resin of the functionality of the more than one epoxide group of per molecule by the amide amine composition of optional part end-blocking and at least one.This epoxy-functional tensio-active agent can be the nonionic surface active agent that original position is formed when reacting with excessive epoxy-functionalized compositions.Epoxy component can be epoxy resin, or the mixture of epoxy resin and phenolic compound.The polyethylene oxide original surface promoting agent that the multiamide of this amide amine composition is amine-functionalized contacts under the condition effectively making amine groups and epoxide group react with epoxy component.

Epoxy-functional tensio-active agent can by under the condition effectively making amine groups and epoxide group react, the polyethylene oxide original surface promoting agent making the multiamide that formed by the original blend of polyoxyalkylene polyol compound amine-functionalized and at least one epoxy component are reacted and are prepared, and this epoxy component has the functionality of the more than one epoxide group of every group.This epoxy component can have the stoichiometric ratio identical with amine groups or equivalence ratio, or can have relative amine groups stoichiometric excess or the excessive ethoxyl substitution of equivalent.The equivalence ratio of amine and epoxide can be at least 1:2, such as, such as, in the scope of about 1:6 to about 1:500, in the scope of about 1:6 to about 1:30.

This reaction typically carrying out under being enough to make the temperature of the rising of amine groups and epoxide group reaction from envrionment temperature, such as, proceeds to the time of effective preparation feedback product at atmosheric pressure in the scope of about 50 DEG C to about 200 DEG C.The progress of reaction can be detected by the epoxy equivalent weights of measurement reaction mixture and its target is to prepare the product expected.Usually, reacting by heating mixture is until the epoxy equivalent (weight) be consumed equals the amine equivalent added, and this is normally one hour or longer.More than the polyethylene oxide original surface active agent response that a kind of epoxy resin can be amine-functionalized with multiamide.

Epoxy component for the preparation of tensio-active agent can be any per molecule on average there is more than one epoxide group have 1, the reactive epoxy resin of 2-epoxy group(ing), oxyethane, Equivalent, and in some applications, have about 1.5 in per molecule to about 6.5 epoxide groups.This epoxy resin can be saturated or unsaturated, line style or branching, aliphatics, alicyclic, aromatic series or heterocycle, and can with not hindering the substituting group with the reaction of carboxylic acid in essence.These substituting groups can comprise bromine or fluorine.Epoxy resin can be monomer or polymerizability, liquid or solid-state, but it is at room temperature preferably liquid or low melting point solid.Usual epoxy component comprises the compound distribution of the repeating unit with varied number.

Suitable epoxy resin comprises and carries out reacting the glycidyl ether prepared under basic reaction conditions by Epicholorohydrin and the compound that comprises at least 1.5 aromatic hydroxyl groups.Be applicable to the example of epoxy resin of the present invention except above-mentioned epoxy resin, also comprise monoepoxide, the diglycidylether of dihydroxy compound, epoxy-Novolak resin, cyclic aliphatic epoxide compound, polycarboxylic many glycidyl esters, containing acrylic resin and their combination of glycidyl methacrylate.

In addition, epoxy component can be the mixture of the epoxy resin of polyethylene oxide original surface active agent response that can be amine-functionalized with multiamide.In such embodiment, epoxy resin can comprise monoepoxy resin and two and/or multi-functional epoxy resin, preferred epoxy has the functionality of about 0.7 to about 1.3, and epoxy resin has the functionality of at least 1.5, be preferably at least 1.7, be more preferably about 1.8 to about 2.5.This mixture or can add simultaneously or react with it with amide amine composition substep.Such as, first the polyethylene oxide original surface promoting agent that the multiamide of amide amine composition is amine-functionalized can react with monoepoxy resin and react with diepoxy resin afterwards.In another example, epoxy component can with phenolic resin varnish and diepoxy resin with any order substep or simultaneous reactions.

If desired, can to reclaim from reaction mixture or " original position " preparation table surface-active agent.In order to provide tensio-active agent at the epoxy component situ expected, the amine-functionalized polyethylene oxide original surface promoting agent of multiamide can be reacted in the epoxy component of expectation.For in-situ method, epoxy component should exist to be enough to provide the amount of unreacted epoxy component and surfactant adduct.

The method of this original position can comprise the amide amine original surface promoting agent providing epoxy-functional that wherein epoxy component residue (hydrophobic part) is identical with disperseed body epoxy resin, this epoxy component and the amine-functionalized polyethylene oxide original surface active agent response of multiamide.When the hydrophobic part from tensio-active agent has the IR spectrum identical with the IR spectrum of body epoxy resin, the residue of epoxy component (hydrophobic part) is identical with body epoxy resin.When reclaiming tensio-active agent, the equivalence ratio of amine and epoxy is preferably in the scope of about 1:30 to about 1:6.

In addition, in order to provide tensio-active agent at epoxy resin (advancedepoxyresin) situ through upgrading, this amide amine composition can be reacted in the mixture of diepoxy resin between the upgrading reaction period together with dihydric phenol, the diglycidylether of described diepoxy resin such as dihydric phenol, or can be reacted in resin after upgrading reaction.In upgrading reaction, usual diepoxy resin and dihydric phenol allow with the molar ratio reaction of about 7.5:1 to about 1.1:1 under the existence of upgrading catalysts, and preparation has the upgrading epoxy resin of the epoxy equivalent (weight) of about 225 to about 3500.Based on epoxy resin, or based on epoxy resin and phenolic compound, the amide amine composition of typical use about 0.1 to about 15 % by weight.Preferably after upgrading reaction, add amide amine composition, no matter whether be separated upgrading product or it provides as upgrading product former state.

Suitable diepoxy resin can comprise difunctional epoxy resin, diepoxy resin, the diglycidylether of such as dihydric phenol, the diglycidylether of hydrogenation dihydric phenol, branching or linear aliphatic glycidyl ether, epoxy-Novolak resin or cycloaliphatic epoxy resin.

The diglycidylether of dihydric phenol such as can react in the presence of base by making Epicholorohydrin and dihydric phenol and prepare.The example of suitable dihydric phenol comprises: 2,2-bis-(4-hydroxy phenyl) propane (bisphenol-A); 2,2-bis-(4-hydroxyl-3-tert-butyl-phenyl) propane; 1,1-bis-(4-hydroxy phenyl) ethane; 1,1-bis-(4-hydroxy phenyl) Trimethylmethane; Two (2-hydroxyl-1-naphthyl) methane; 1,5-dihydroxy naphthlene; 1,1-bis-(4-hydroxyl-3-alkyl phenyl) ethane and similar substance.Suitable dihydric phenol can also be obtained by the reaction of phenol and aldehyde such as formaldehyde (bisphenol-f).The glycidyl ether of dihydric phenol comprises the diglycidylether of above dihydric phenol and the upgrading product of dihydric phenol (such as bisphenol-A), such as, by reference to being incorporated to U.S. patent Nos.3 of the present invention, 477,990 and 4,734, in 468 describe those.

Such as, can hydrogenation dihydric phenol be passed through, under the existence of Lewis acid catalyst, carry out glycidated reaction with Epicholorohydrin afterwards, and form glycidyl ether and the diglycidylether preparing hydrogenation dihydric phenol by reacting with sodium hydroxide afterwards.The example of suitable dihydric phenol be listed above those.

Such as, can react under the existence of Lewis acid catalyst by making Epicholorohydrin and branching or linear aliphatic glycol or aromatic diol, and be converted into glycidyl ether by halohydrin intermediates prepare aliphatic glycidyl ether by reacting with sodium hydroxide afterwards.The example of preferred aliphatic glycidyl ether comprises corresponding to those of following formula:

Wherein:

P is the integer of 1 to 12, is preferably 1 to 4,

Q is the integer of 4 to 24, is preferably 4 to 12, and

R ₁₁can be the bivalent cycloaliphatic group with following structure and formula:

or

Wherein R ₁₂and R ₁₃separately independently for having the alkylen group of following formula, or divalent aryl aliphatic group:

Wherein R ₁₄it is alkylen group.Term aliphatics or be alicyclicly included in the compound in main chain or on main chain with oxygen and/or sulphur atom.

The example of suitable aliphatic glycidyl ether such as comprises 1,4-butyleneglycol, cyclohexanedimethanol, hexylene glycol, polypropylene glycol and similar glycol with the diglycidylether of glycols, also comprise the triglycidyl ether of trimethylolethane and TriMethylolPropane(TMP).

Epoxy-Novolak resin can by formaldehyde and phenol condensation, glycidatedly by reacting in the presence of base with Epicholorohydrin more afterwards prepares.Phenols can be such as phenol, methylphenol, nonylphenol and tert.-butyl phenol.The example of preferred epoxy-Novolak resin comprises corresponding to those of following formula:

Wherein R ₇be hydrogen atom or C independently ₁-C ₁₀alkyl group and r is the real number of 0-6.Epoxy-Novolak resin comprises the compound distribution of the glycidated phenol oxymethylene units r with different number usually.Usually, the number of unit quoted is the numeral of the peak value being similar to statistics mean value and distribution.

Cycloaliphatic epoxides can by having preparing with carboxylic acid peroxide's (such as peracetic acid) epoxidation containing cyclic olefins of more than one ethylene linkage.The example of preferred cycloaliphatic epoxides comprises corresponding to those of following formula:

or

Wherein R ₁₀aliphatic divalent group optionally containing ether or ester group or itself and R ₉or R ₈formed optional containing heteroatomic volution together, R ₉and R ₈be independently hydrogen atom, or R ₉or R ₈with R ₁₀formed optional such as, containing heteroatomic volution, Sauerstoffatom together.Preferred R ₁₀containing 1 to 20 carbon atoms.The example of cycloaliphatic epoxides such as comprises: 3,4-epoxycyclohexylmethyl-(3,4-epoxy group(ing)) cyclohexane carboxylate; By 4-tetrahydrobenzene formaldehyde and the tetramethylolmethane condensation of about 2 moles, make bicyclic oxygen spiral shell diethyl acetal prepared by double bond epoxidation afterwards again; Two (3,4-epoxycyclohexylmethyl) adipic acid ester, two (3,4-expoxycyclohexyl) adipic acid esters and vinyl cyclohexene titanium dioxide [4-(1,2-epoxy group(ing) ethyl)-1,2-epoxy-cyclohexane].Cycloaliphatic epoxides comprises the compound of following structure and formula:

The example of the preferred epoxy of business such as comprises and being all obtained commercially by MomentiveSpecialtyChemicalsofColumbusOhio resinsDPL-862,828,826,825,1001,1002, resin1510, modifiers32,62,63,64,65,67,68,71,107,116, resinDPS155, resinHPT1050 and resinE-10, also comprises the EpoxyResinsERL-4221 ,-4289 ,-4299 ,-4234 and-4206 be obtained commercially by UnionCarbide.

The reaction of amide amine composition as above and epoxy component forms epoxy-functional tensio-active agent.For the formation of original position epoxy-functional tensio-active agent, such as in excessive epoxy component or aqueous dispersion, epoxy-functional tensio-active agent accounts for about 1wt.% of final composition to about 20wt.%, and such as approximately 1wt.% is to about 10wt.%, and such as about 1wt.% is to about 4wt.%.

In an embodiment of epoxy-functional tensio-active agent, this tensio-active agent can have following formula:

And m can be 1 to 11, n can be 1 to 3, q can be 0 to 8, such as 0 to 4, and p can be about 18 to about 500.X can be hydrogen atom, methyl substituents, ethyl substituent, hydroxymethyl substituents, their subset or their combination.Each Y can be hydrogen atom, methyl substituents, ethyl substituent, hydroxymethyl substituents, their subset or their combination.R ₁₇can be alkyl group, aromatic yl group, carboxyl groups and their combination of their subset sums.R ₁₇may further include 1 to 50 carbon atoms, and may further include oxygen, nitrogen and sulphur atom.

Epoxy-functional tensio-active agent can have following formula:

For repeating unit, m can be 1 to 3, n can be 1.2, q can be 1.9 to 2.3, and p can be about 81 to about 210.X can be hydrogen atom or methyl substituents.Each Y can be hydrogen atom or methyl substituents.R ₁₇it can be tertiary carboxyl groups.

Epoxy-functional tensio-active agent can be converted into amine-functionalized compound.This amine-functionalized compound can be used as the solidifying agent of epoxy composite or be used as tensio-active agent for amine polymer composition.Solidifying agent as described in the present invention can by the epoxy-functional tensio-active agent that makes the present invention describe and at least one amine component, the amine component reaction that such as the present invention describes and preparing.

Described at least one amine component can comprise polyamines.Polyamines can have at least one primary amine group and at least one secondary amine group.The non-limiting example with the polyamine compounds of the first and second amine groups is represented by following formula:

H ₂n-R ₁₆-[NH-R ₁₆] _n-NH ₂(V), and

For repeating unit, n can be the mean number of integer between 1 to 10, is preferably between 1 to 4, and R ₁₆there is the divalence branching of 1 to 24 carbon atoms or non-branched hydrocarbyl radical, one or more aryl or kiki fang alkyl group, or one or more alicyclic groups, condition is that initial polyamine compounds has 2 to 18 carbon atoms.Preferably, R ₁₆the lower alkylene group with 1 to 10 carbon atoms, such as 2 to 6 carbon atoms.

The example of polyamine compounds comprises ethylene, butylidene polyamines, propylidene polyamines, pentylidene polyamines, hexylidene polyamines, sub-heptyl polyamines and their combination.In the piperazine that the higher homologue of these amine and relevant aminoalkyl group replace is also included within.The specific examples of polyamines comprises 1, 2-diaminoethanes, three (2-amino-ethyl)-amine, 1, 2-and 1, 3-diaminopropanes, 1, 2-and 1, 4-butane diamine, 2-methyl isophthalic acid, 5-pentane diamine, 1, 6-hexane diamine, 1, 10-decanediamme, 1, 8-octanediamine, 1, 4, 7-triazaheptane, 1, 4, 7, 10-tetra-azepine decane, 1, 9, 17-tri-azepine heptadecane, 2, 5, 8-trimethylammonium-1, 4, 7, 10-tetra-azepine decane, 1, 4, 7, 10, 13-pentaaza tridecane, 1, 4, 7, 10, 13, 16-six azepine n-Hexadecane, 1, 5, 9-tri-azepine nonane, 1, 3-and 1, 4-bis-(amino methyl) benzene, 4, 4 '-diaminodiphenyl-methane, 2, 4-diaminostilbene-methylbenzene, 2, 6-diaminostilbene-methylbenzene, polymethylene polyphenyl amine, 1, 2-diamino-cyclohexane, 1-amino-3-(amino methyl)-3, 5, 5-trimethyl-cyclohexane, 1, 3-bis-(amino methyl) hexanaphthene, 4, 4'-diamino-dicyclohexyl methane and their combination.The higher homologue that the condensation of the alkylene amine listed by two or more is obtained can also be used.

The solidifying agent that the present invention describes can be prepared to react under the ratio of active amine hydrogens atom and the epoxide group ratio that is 2:1 or higher by making epoxy-functional component and at least one amine component, such as about 5:1 is to about 30:1, or such as approximately 5:1, to about 15:1, prepares the product of amido end-blocking thus.The solidifying agent that the present invention describes has the amine nitrogen atom equivalent weight of at least 50, and preferably at least 65, such as about 100 to about 400.

In addition, amine-functional compounds can use mono-epoxy compounds, and this effectively makes remaining active amine hydrogens atom and epoxide group before the dispersing or react under disperseing post-reacted condition and carry out by making compound.The product of amine end-blocking can with monoepoxide to react the product providing end-blocking under the ratio of remaining active amine hydrogens atom and the epoxide group ratio that is 3:1 or higher, such as approximately 5:1 to about 10:1, such as about 8:1.The time period of effective preparation feedback product is typically reacted in this reaction under about 50 DEG C to the temperature within the scope of about 100 DEG C.Usually, reacting by heating mixture is until the amine equivalent consumed equals epoxy equivalent (weight) (substantially all epoxide groups have all consumed).

In embodiment second month in a season of amine-functional compounds, amine-functional compounds can have following formula and m can be 1 to 11, n can be 1 to 2, q can be 0 to 8 and p can be about 45 to about 500:

X can be hydrogen atom, methyl substituents, ethyl substituent, hydroxymethyl substituents, their subset or their combination.Each Y can be hydrogen atom, methyl substituents, ethyl substituent, hydroxymethyl substituents, their subset or their combination.R ₁₇can be alkyl group, aromatic yl group, carboxyl groups and their combination of their subset sums.R ₁₇may further include 1 to 50 carbon atoms, and may further include oxygen, nitrogen and sulphur atom.

In addition, can by mono-epoxy compounds and polyamines simultaneously or in succession introduce to make any pending substituted radical react to form amine-functional compounds further.This mono-epoxy compounds can be any one in the mono-epoxy compounds that describes of the present invention.The specific examples of monoepoxide end-capping reagent is included in alkyl chain the alkyl glycidyl ether with 1-18 Linear carbon atom, such as butylglycidyl ether, or C ₈-C ₁₄the mixing glycidyl ether of alkyl, toluene glycidyl ether, phenyl glycidyl ether, nonyl phenyl glycidyl glyceryl ether, to tert-butyl-phenyl glycidyl ether, 2-hexyl glycidyl ether, the glycidyl ester of neodecanoic acid and their combination.

In addition, the solidifying agent that the present invention describes can disperse in aqueous.This dispersion can comprise the solidifying agent of water and the present invention's description.This composition can provide by being mixed in solidifying agent by water when presence or absence tensio-active agent before capping or after end-blocking.Any for making solidifying agent emulsification or dispersion conventional surfactants in aqueous use.But the solidifying agent that the present invention describes makes self emulsifiable and without any need for extra tensio-active agent to provide aqueous solidified agent solution, emulsion or dispersion.

Amine-functional compounds also refers to amine-functionalized adduct polymerization thing, it can be dispersed in water to obtain transparent (white) dispersion, this dispersion has the average micron diameter particle diameter Dv of about 0.2 to about 1, such as about 0.516, and Sa is about 0.2 to about 0.7, such as about 0.423.Non-volatile content in this dispersion can be about 50% to about 55%, such as about 51.6%, and the amine value of non-volatile amine polymer can be about 225 to about 275, such as about 257.The epoxy dispersion conbined usage that this amine-functionalized polymers dispersion can describe with the present invention, to prepare high-performance priming paint, such as, describes in embodiment 18.

The solidifying agent that the present invention describes can former state, in organic solvent or in water for solidifying liquid state or solid epoxy resin.The solidifying agent that any epoxy resin of the solidifying agent that preparation the present invention that the present invention describes describes can be described by the present invention solidifies.This solidifying agent may be used for environment coatings applications and baking coatings applications.Solidification value can depend on application and change, and it is typically in the scope of about 5 DEG C to about 200 DEG C.

These solidifying agent that the present invention describes can effectively for Curing Waterborne Epoxy Resin system.Preferred aqueous epoxy resin systems is that the nonionic of the molecular weight with 350 to about 10000 is dispersed in water and has or do not have the bisphenol-A base epoxy of glycol ethers cosolvent.The example that is purchased of aqueous epoxy resins such as comprises the EPI-REZ obtained by MomentiveSpecialtyChemicals, Inc ^tMresin3520,3522,33540 and 5522.The solidifying agent that the present invention describes does not use acid-salt can be compatible with aqueous dispersion yet.These curable systems comprise the solidifying agent that water, one or more epoxy resin and one or more the present invention describe.These aqueous curable epoxy-resin systems can at room temperature or at elevated temperatures solidify, or it can further with the Tertiary amine accelerators catalytic curing of commercially available acquisition, such as 2,4,6-tri-(dimethylaminomethyl phenol) or other phenols are to solidify at a lower temperature.The example of these materials has the EPI-KURE from MomentiveSpecialtyChemicals, Inc. ^tMcuringAgent3253 or the DMP-30 from RohmandHaas.These low temperature are typically in the scope of about 5 DEG C to about 20 DEG C.For aqueous epoxy resin systems, use or do not use the typical solidification value of promotor all in the scope of about 5 DEG C to about 200 DEG C.These solidifying agent are typically for preparing the thermosetting coating substrate of coating to good non-corroding protective.

aqueous epoxy resins dispersion

The epoxy resin that water-base epoxy dispersion can comprise water, at least one the present invention describes and the amine-functionalized polyoxyalkylene original surface promoting agent of multiamide, this original surface promoting agent described at least one epoxy resin epoxy-functional in position, and can before contacting with the described at least one epoxy resin of described dispersion epoxy-functional.

The aqueous epoxy resins dispersion that the present invention described above is formed shows the character of the multiple improvement higher than prior art dispersion.The character improved is the shelf stabilities of the improvement that stability, the pH stability of improvement and the viscosity stability of improvement improved by epoxy component is confirmed.

On the one hand, compared with not blended composition of the prior art, for the blend of the tensio-active agent of the epoxy resin dispersion described for the formation of the present invention based on the present invention, observe that improve along with the time or suitable with it viscosity.In an example, observe, by the composition of the polyoxyalkylene polyol the comprising acid blocked aqueous epoxy resins dispersion that amidation is formed altogether, there is after the storage of 8 months the viscosity being less than 1700cps, be less than 1800cps after 10 months and be less than 1900cps after 15 months, said composition is the blend of 55:45 of the polyoxyethylene glycol component of the 4000Mw/8000Mw molecular weight formed in following examples 10.By contrast, based on the composition of the polyoxyethylene glycol of 4000MW with show based on the composition of the polyoxyethylene glycol of 4600MW the viscosity being greater than 4000cps after 8 months separately.

The aqueous dispersion observing the present invention's formation, in double viscosity or the time period more than 6000cps, has the pH unit change of about 0 to about 3.Other examples of these improvement projects are shown in embodiments described herein and form.

On the one hand, average particle size particle size in the aqueous epoxy resins dispersion formed here that the present invention describes is less than the order of magnitude of 1.50 μm dimensionally, such as about 0.2 to about 1.2 μm, such as about 0.65 to about 0.87 μm, and it can be comparable with the size of about 0.74 to 0.88 of prior art.Use particle size little as far as possible to obtain the cohesiveness of economy and the improvement improved when being desirably in epoxy polymer content high as far as possible, obtain best film mechanical properties and chemical property thus.

Describe according to the present invention in the typical aqueous dispersion of application of paints, based on total dispersion, the amount (being also known as the content of solids content or non-volatile substance) comprising the epoxy resin ingredient of epoxy-functional tensio-active agent can for about 20 to about 75% weight, and preferably approximately 55 is to about 65% weight.Usually, based on the weight of solid, water and have the epoxy resin of per molecule more than 0.8 epoxy functionalities at above-mentioned epoxy-functional tensio-active agent with about 1wt% to about 6wt%, such as about 2wt% to about 5wt%, such as approximately 3.5wt% deposits in case to the amount be less than within the scope of 4.5wt%, mixes under the condition effectively providing O/w emulsion.If the efficiency of epoxy-functional tensio-active agent of the present invention improves, then the amount required for central dispersion epoxy resins just reduces.

From epoxy-functional tensio-active agent, confirm separately that epoxy resin is easily, this is only because epoxy-functional tensio-active agent can original position preparation in the epoxy.This dispersion can by adding to tensio-active agent and water in epoxy resin to disperse or to be prepared by " original position " preparation table surface-active agent described above.These dispersions can also be prepared by being added to by epoxy resin in described amide amine composition and water.This tensio-active agent can by the temperature effectively making amide amine and epoxy resin reaction amine-functionalized for multiamide polyoxyalkylene original surface promoting agent to be added in epoxy resin or by before upgrading reaction as mentioned above or period polyoxyalkylene original surface promoting agent that multiamide is amine-functionalized add original position in difunctional epoxy's resin and dihydric phenol to and prepare.

One or more epoxy-functional amide amine original surface promoting agents can be used.Optionally, cosurfactant can use together with epoxy-functional tensio-active agent.Optionally, dispersion also comprises acetone.In one embodiment, dispersion comprises acetone and the non-volatile hydrophobic liquid resin of at least one or modifier.Acetone can exist with the amount of about 0.5wt.% or higher, more preferably exists with the amount of about 1wt.% to about 3wt.%, such as about 1.5wt.%.

Useful coating composition can pass through the functionalized epoxy curing agent of mixed amine and above-mentioned aqueous epoxy resins dispersion obtains.Aqueous epoxy resins dispersion described above and solidifying agent can as the components of the paint and coating that are applied to substrate, such as, and metal and cementaceous works.In order to drive coating composition to complete, the coating that can be obtained by these dispersions can also be heated about 30 to about 120 minutes at elevated temperatures, preferably in the scope of about 50 DEG C to about 120 DEG C.

In order to prepare this paint and coating, main and the expanding material of aqueous epoxy resins dispersion and/or solidifying agent and corrosion-inhibiting pigment, and optional and additive, such as tensio-active agent, defoamer, rheology modifier and stain control agent (mar) and lubricant (slipreagent) are blended.The epoxy-resin coating composite that the present invention describes can comprise other additives, such as elastomerics, stablizer, expanding material, softening agent, pigment paste, oxidation inhibitor, levelling or thickening material and/or cosolvent, wetting agent, cosurfactant, reactive diluent, filler, catalyzer and their combination.What the selection of these pigment and additive and its consumption depended on paint has a mind to application and normally well known by persons skilled in the art.

Reactive diluent can be any non-volatile, hydrophobic compound, and it is at room temperature liquid and flowable, no matter it is former state or in hydrophobic solvent, and such as dimethylbenzene or butanols.When something meets the definition according to ASTMD2369-93 or ASTMD3960-93, it is exactly nonvolatile.For coating composition, reactive diluent (being also known as hydrophobic liquid resin or modifier) compatiblely with the solidifying agent in coating composition (such as must can not damage erosion resistance, or high-luster etc.), described solidifying agent such as, amine hardener.

Based on the total amount of component, reactive diluent can exist with the amount of about at most 25wt.%, and such as about 1 to about 10wt.%.Preferred reactive diluent such as comprises aliphatic monoglycidyl ethers, urea-formaldehyde resin or aliphatics list glycidyl ester.Preferred monoepoxide diluents comprises not miscible with water glycidated C _8-20fatty alcohol, C _1-18those of alkylphenol glycidyl ether or glycidated tertiary carboxylic acid.Monoepoxide component can comprise alicyclic and aromatic structure, and halogen, sulphur, phosphorus and other such heteroatomss.Reactive diluent can be such as epoxidation unsaturated hydrocarbons, such as decene oxide and cyclohexene oxide; The glycidyl ether of single hydroxyl alcohol, such as 2-Ethylhexyl Alcohol, dodecanol and eicosanol; The glycidyl ester of monocarboxylic acid such as caproic acid; The acetal of glycidaldehyde and similar substance.Preferred reactive diluent is monohydroxy C _8-14the glycidyl ether of fatty alcohol.Reactive diluent can be by the commercially available HELOXY of MomentiveSpecialtyChemicals ^tM7Modifier (C ₈– C ₁₀alkyl glycidyl ether), HELOXY ^tM9Modifier (C _10-11alkyl glycidyl ether) and by the commercially available CYMELUF of CytecIndustriesInc ^tM216-10Resin (alkylation urea aldehyde high solid solution).Aqueous dispersion can also comprise the monoepoxide diluents as reactive diluent.

The example of main pigments comprises rutile titanium dioxide, such as, obtained by DuPont 2160 (Kronos, Inc.) and r-960, yellow titanium dioxide, red iron oxide, Yellow iron oxides and carbon black.The example of expanding material pigment comprises calcium metasilicate, such as 10ES (NYCOMinerals, Inc.), barium sulfate, such as (HarcrosPigments, Inc.) and pure aluminium silicate, such as 170 (EnglehardCorp.).The example of erosion resistance pigment comprises phosphorus Calucium Silicate powder strontium, such as HALOXSW111 (HaloxPigments), the aluminium triphosphate of zine ion modification, such as 84 (TaycaCorp.) and alkali formula aluminum phosphate zinc hydrate, such as zPA (HeucoTech, Ltd.).

Extra tensio-active agent can be included in improve soaking of pigment and substrate in waterborne epoxy paint and coating.These tensio-active agents typically non-ionic type, the example comprises x-100 and TRITONX-405 (DowChemicalCompany) and 104 (AirProductsandChemicals).

Defoamer and defrother suppress the generation of foam during paint or coating manufacture.Useful defoamer comprises l-475 (DrewIndustrialDiv.), pF-4Concentrate (UltraAdditives) and 033 (BYK-Chemie).

Rheologic additive is for obtaining suitable application performance.Have the additive of three types provide required by waterborne epoxy coating thickening and shear shinning, that is, Natvosol, organically-modified HECTABRITE DP and associative thickener. 250MBR and NATROSOLPlus (Aqualon) be the Natvosol class of modification example and lT (RHEOX, Inc.) is the representative example of HECTABRITE DP.Optiflo ^tM(SouthernClay) be useful associative thickener.

Stain control agent (Mar) and lubricant improve in early days to the tolerance of the wearing and tearing from scraping or light footmark (lightfoottraffic).Polydimethylsiloxane and polyethylene oxide wax are used for this on the one hand.Commercially available wax lubricant is MICHEM 182 (MICHELMAN, INC.).

Curable paint and coating composition can be applied to substrate by brushing, spraying or roller.Aqueous dispersion of the present invention can also be used as the component of tackiness agent and fiber sizing material.

Other purposes of the original surface promoting agent described for the present invention, tensio-active agent, aqueous dispersion and solidifying agent can comprise the humid control film for curing concrete and the rare tackiness agent for multiple layer metal laminate.

In addition, epoxy curing agent can be the solidifying agent that any effective solidification (or crosslinked) is dispersed in the epoxy resin in aqueous solution, comprises the solidifying agent prepared by epoxy-functional amide amine original surface promoting agent of the present invention.Described solidifying agent normally can be compatible with water (namely dilutable and/or dispersible).

Other suitable solidifying agent used together with dispersion or co-curing agent comprise those that typically use together with epoxy resin, such as aliphatics, aromatic yl aliphat and aromatic amine, polyamines, amide amine and epoxy-amine adducts, melamino-formaldehyde resin and fluosite.This solidifying agent shows the water-compatible of different levels, and this depends on the characteristic of the starting raw material of the preparation for them.

Preferably, in order at room temperature or at lower temperature solidify, other suitable solidifying agent or co-curing agent can have the epoxy equivalent (weight) of about 1:0.75 to about 1:1.5 and the portfolio ratio of amine hydrogen equivalent.These other suitable solidifying agent or co-curing agent is available comprises polyoxyalkylene amine hardener, it is for water soluble or be dispersed in water and comprise more than those of 2 active hydrogen atoms in per molecule, such as diethylenetriamine, Triethylenetetramine (TETA), tetraethylenepentamine etc.The example comprises 1, 6-hexane diamine, 1, 3-pentane diamine, 2, 2 (4), 4-trimethylammonium-1, 6-hexane diamine, two (3-aminopropyl) piperazine, N-aminoethyl piperazine, N, N '-two (3-aminopropyl) quadrol, 2, 4 (6)-tolylene diamines, and comprise cycloaliphatic amines, such as 1, 2-diamino-cyclohexane, 1, 4-diamino-2, 5-diethyl cyclohexane, 1, 2-diamino-4-ethylcyclohexane, 1, 2-diamino-4-cyclohexyl ring hexane, isophorone diamine, norcamphane diamines, 4, 4'-diamino-dicyclohexyl methane, 1, 1-bis-(4-aminocyclohexyl) ethane, 2, 2-bis-(4-aminocyclohexyl) propane, 3, 3'-dimethyl-4, 4'-diamino-dicyclohexyl methane, 3-amino-1-(4-aminocyclohexyl) propane, 1, 3-and 1, 4-bis-(amino methyl) hexanaphthene, and their combination.As aromatic aliphatic amine, the wherein amino group particularly used is present in those amine on aliphatic group, such as m-and to two xylene diamines or their hydrogenated products.Described amine can be used alone or uses as mixture.

For the cure applications of comparatively high temps, aminoplast(ic) resin can be used as the solidifying agent of the epoxy resin with equivalent weight, such as, higher than 700.Based on the combination weight of epoxy resin and aminoplast(ic) resin, usually use about 5 to about 40, such as about 10 to about 30, such as about aminoplast(ic) resin of 30 % by weight.Suitable aminoplast(ic) resin is that urea and melamine and aldehyde are in some cases further by etherified reaction product.The example of aminoplast(ic) resin component is urea, ethylidene-urea, thiocarbamide, melamine, benzoguanamine and acetyl trimeric cyanamide.The example of aldehyde comprises formaldehyde, acetaldehyde and propionic aldehyde.Aminoplast(ic) resin can alkanol form use, but preferably it uses with the form of ether, wherein etherifying agent is the single hydroxyl alcohol comprising 1 to 8 carbon atoms.The example of suitable aminoplast(ic) resin is methylolurea, dimethoxy methylolurea, butylated polymerizability urea-formaldehyde resins, six (methoxymethyl) melamine, methylated polymerizability melamine-formaldehyde resin and butylated polymerizability melamine-formaldehyde resin.

The example that is purchased of water-compatible solidifying agent comprises EPI-CURE ^tM8540,8537,8290 and 6870CuringAgents (can be obtained by MomentiveSpecialtyChemicals), ANQUAMINE401, Casamid360 and 362 solidifying agent (AirProducts); HardenerHZ350, Hardeners92-113 and 92-116 (Huntsman); BECKOPOXEH659W, EH623W, VEH2133W solidifying agent (Cytec) and EPOTUF37-680 and 37-681 solidifying agent (ReichholdChemicalCo.).

Curable composition epoxy resin can solidify the time period effectively making epoxy resin cure at about 5 DEG C at the temperature in the scope of about 200 DEG C, such as 20 DEG C to about 175 DEG C.

Embodiment

There is provided following examples for illustration of some embodiment as described in the present invention.These embodiments are not intended to the scope of restriction application and should carry out such explanation explanation to them.Except as otherwise noted, amount is all with weight part or parts by volume or weight percentage or volume percent.

Testing method

The emulsion obtained or dispersion measure viscosity by the BrookfieldSynchroLectricViscometer from BrookfieldEngineeringLaboratories.

The mensuration of emulsion and dispersion particle size uses the BrookhavenBi-DCPParticleSizer from BrookhavenInstrumentsCorporation and CoulterLS230 to complete, except as otherwise noted.Dn is number average bead diameter, and Dw is weight average particle diameter, and Dv is volume average size diameter and Sa is surface-area median size.All Particle size data are all in micron μm.

Amine value reporting is the milligram number with the KOH of the basic n content equivalence of one gram of sample, and its acid-base titration by ASTMD2896 testing method measures.

Acid equivalent weight/carboxyl equivalent weight is measured by ASTMD1639 test process.

The nitrogen equivalent weight of amine is calculated in batch by the reagent equivalent weight that uses and every quality of lot balance in theory.

Epoxy equivalent weights is measured by the test process of ASTMD1652 and D4142.

Composition and for the formation of composition method example as follows listed by.

Embodiment 1A is the comparative example that the composition of prior art and oxidation have the method for the polyoxyethylene glycol (PEG) of 4600 number-average molecular weights and high carboxyl level (U.S. patent 6,956,086B2 embodiment 1).

The water of PEG4600 and 45.4Kg of 601.5Kg is added to form mixture in the stainless steel reactor with about 1150 liters of capacity.This mixture is heated to 60 DEG C and stirs to dissolve PEG.Then under agitation the nitric acid of 67% of 7.14Kg and the mixture of the water of 21.9Kg and 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxygen base free radical (4-hydroxyl TEMPO) of 5.41Kg are loaded in reactor.Then closed reactor exports and is joined in reactor by oxygen.Adding enough oxygen makes reactor reach and the oxygen pressure keeping also having in addition to air 25psig (172kPa), and described air was just present in reactor before adding oxygen.The oxygen pressure added by being set in maintenance from steel cylinder along with extra oxygen is that the setter of 172kPa adds, and under agitation makes reactor keep 4 hours at 57-63 DEG C.Now, steel cylinder pressure reduces 1975psig (13.62MPa), and this shows that the oxygen of 8.38Kg is transferred in reactor from steel cylinder.Then Oxygen Flow and at this temperature along with stirring reaction continues extra two hours to consume the most of oxygen in reactor head space is closed.

In this time period Mo, the oxygen pressure joined in reactor head space is reduced to 9.6psig (66kPa) and the wear rate of oxygen becomes very low.Discharge remaining oxygen and vacuum application is reduced to 13.5kPa in reactor to make absolute pressure.Temperature of reactor is elevated to 93 DEG C with distilled water and is retained in the liquid trap of top by nitric acid.Distillation continues 1.5 hours.Break vacuum and product being sampled with regard to acid equivalent weight.This acid equivalent weight is 2382, and it corresponds to the alcohol end group oxidation of 93%.Emptying top liquid trap.The PEG of this oxidation for the preparation of contrast in embodiment 4, the multiamide amine original surface promoting agent of prior art level.

Embodiment 1B is the high carboxyl Horizontal oxide embodiment of the polyoxyethylene glycol (PEG) with 4600 number-average molecular weights.

To there is the water of the PEG4600 (having the hydroxyl equivalent weight of 2300) and 2.53Kg that add 30Kg in the stainless steel reactor of about 57 liters of capacity to form mixture.This mixture is heated to 60 DEG C and stirs to dissolve PEG.Then under agitation by the nitric acid of 67% of 0.18Kg and the mixture of the water of 0.45Kg and the 4-hydroxyl TEMPO loading reactor of 0.54Kg.Then closed reactor exports and is joined in reactor by oxygen from the steel cylinder with setter.Add enough oxygen to make reactor reach and to remain on the oxygen pressure also having 25psig (170kPa) in addition to air, described air was just present in reactor before adding oxygen.The oxygen pressure added by being set in maintenance from steel cylinder along with extra oxygen is that the setter of 170kPa adds, and under agitation reactor keeps 9.5 hours at 60 DEG C.Timing sampling and to the sample of the drying carboxyl equivalent weight by titration determination solid fraction (itself then may be used for calculating oxidation percentage ratio) from reactor.

Take out final sample after 9.5 hours and stop when the sample is analyzed in oxygen inflow reactor.The titration of dry sample shows the carboxyl equivalent weight of 2440, and it corresponds to the oh group of 94.3% to the transformation efficiency of carboxyl.When obtaining analytical results, the oxygen in emptying reactor and use purging with nitrogen gas reactor.

Then, along with reactor pressure is reduced to about 1700Pa, temperature of reaction is elevated to about 105 DEG C.Water and other volatile matter are distilled about 3 hours until distillating of distillment stops in fact from reactor.Then the molten product remained in reactor is all loaded in multiple keg.Without issue dry time product have 2410 acid equivalent weight and at 150 DEG C in air oven the sample of dry 15 minutes there is the acid equivalent weight of 2440.The hydroxyl end groups that the value of the latter corresponds to 94.7% is converted into the degree of oxidation of carboxyl.

Embodiment 2 is high carboxyl Horizontal oxide embodiments of the polyoxyethylene glycol (PEG) with 4000 number-average molecular weights.

To there is the water of the PEG4000 (having the hydroxyl equivalent weight of 2085) and 2.95Kg that add 30Kg in the stainless steel reactor of about 57 liters of capacity to form mixture.This mixture is heated to 60 DEG C and stirs to dissolve PEG.Then under agitation by the nitric acid of 67% of 0.18Kg and the mixture of the water of 0.45Kg and 4-hydroxyl TEMPO (being dissolved in the water of 1.06Kg) the loading reactor of 0.57Kg.Then closed reactor exports and is joined in reactor by oxygen from the steel cylinder with setter.Add enough oxygen to make reactor reach and to remain on the oxygen pressure also having 35psig (240kPa) in addition to air, described air was just present in reactor before adding oxygen.The oxygen pressure added by being set in maintenance from steel cylinder along with extra oxygen is that the setter of 240kPa adds, and under agitation reactor keeps 5.5 hours at 56-61 DEG C.Timing sampling and to the sample of the drying carboxyl equivalent weight by titration determination solid fraction (itself then may be used for calculating oxidation percentage ratio) from reactor.

After 5.25 hours, the carboxyl equivalent weight of solid fraction is 7620, and it corresponds to the oh group of 27.4% to the transformation efficiency of carboxyl.In order to improve rate of oxidation, after 5.5 hours, oxygen pressure is brought up to 50psig (the pressure height 345kPa than initial air).Before reactor termination reaction in emptying and latter stage, reaction continues extra one hour at an elevated pressure.

Then, make reactor be pressurized to higher than atmospheric 50psig (345kPa) and again be heated to 56-61 DEG C with oxygen, along with stirring, mixture keeps extra 4.5 hours at this temperature and oxygen pressure.In this time period Mo, sample and stop when the sample is analyzed in oxygen inflow reactor.The carboxyl equivalent weight of the titration display 2597 of dry sample, it corresponds to the oh group of 80.3% to the transformation efficiency of carboxyl.When obtaining analytical results, the oxygen in emptying reactor and use purging with nitrogen gas reactor.Then dilute with water product makes solids content be 52% (suppressing the crystallization of the oxidation PEG from solution) and be loaded into from reactor in multiple keg.The titration of the dry sample of the finished product shows the carboxyl equivalent weight of 2416, and it corresponds to the oh group of 86.3% to the transformation efficiency of carboxyl.The PEG of this oxidation for the preparation of describe in embodiment 5 with the multiamide amine original surface promoting agent in blend in embodiment 7.

Embodiment 3 is high carboxyl Horizontal oxide embodiments of the polyoxyethylene glycol (PEG) with 8000 number-average molecular weights.

To there is the water of the PEG8000 (having the hydroxyl equivalent weight of 4057) and 2.95Kg that add 30Kg in the stainless steel reactor of about 57 liters of capacity to form mixture.This mixture is heated to 60 DEG C and stirs to dissolve PEG.Then as in Example 2, under agitation by the nitric acid of 67% of 0.18Kg and the mixture of the water of 0.45Kg and 4-hydroxyl TEMPO (being dissolved in the water of 1.06Kg) the loading reactor of 0.57Kg.Then closed reactor exports and is joined in reactor by oxygen from the steel cylinder with setter.Add enough oxygen reactor is reached and remains on the oxygen pressure also having 50psig (345kPa) in addition to air, described air was just present in reactor before adding oxygen.The oxygen pressure added by being set in maintenance from steel cylinder along with extra oxygen is that the setter of 345kPa adds, and under agitation reactor keeps 5.8 hours at 56-61 DEG C.Timing sampling and to the sample of the drying carboxyl equivalent weight by titration determination solid fraction (itself then may be used for calculating oxidation percentage ratio) from reactor.After 5 hours, the carboxyl equivalent weight of solid fraction is 7114, and it corresponds to the oh group of 57.0% to the transformation efficiency of carboxyl.After 5.8 hours, emptying reactor and in termination reaction in latter stage.

And then sample to be taken out and the carboxyl equivalent weight of solid fraction is 6158, its to fortune about 65.9% oh group to the transformation efficiency of carboxyl.Make reactor be pressurized to higher than atmospheric 50psig (345kPa) and again be heated to 56-61 DEG C with oxygen, along with stirring, mixture keeps extra 2 hours at this temperature and oxygen pressure.In this time period Mo, take out sample and stop when the sample is analyzed to the Oxygen Flow in reactor.The carboxyl equivalent weight of the titration display 4995 of dry sample, it corresponds to the oh group of 81.2% to the transformation efficiency of carboxyl.When obtaining analytical results, the oxygen in emptying reactor and use purging with nitrogen gas reactor.Then dilute with water product makes solids content be 52% (suppressing the crystallization of the oxidation PEG from solution) and be loaded in keg from reactor.The titration of the dry sample of the finished product shows the carboxyl equivalent weight of 4940, and it corresponds to the oh group of 82.1% to the transformation efficiency of carboxyl.The PEG of this oxidation for the preparation of describe in embodiment 6 with the multiamide amine original surface promoting agent in blend in embodiment 7.

Embodiment 4A is the comparative example using the product of embodiment 1A to prepare the amide amine original surface surfactant composition of prior art as starting raw material (U.S. patent 6,956,086B2 embodiment 1).

Be cooled to 68 DEG C after reactor content in embodiment 1A and afterwards by the 2-methyl isophthalic acid of 123.1Kg, 5-pentane diamine, DytekA loads in reactor.Within the time period of 2.5 hours, temperature of reactor is elevated to 202 DEG C, allows the mixture of water and some diamines to distill at atmosheric pressure simultaneously.When reactor content reaches this temperature, emptying top liquid trap and application of vacuum are to remove remaining diamines.After 2.75 hours, reactor pressure is 3kPa, and temperature is 209 DEG C and uses nitrogen bubble to promote removing of excessive diamines.This subtractive process continues extra 4.5 hours in vacuum and nitrogen.Break vacuum and sampling reactor content, its amine nitrogen equivalent weight is 2905.

Then by reactor cooling to 104 DEG C and the water loading 317.6Kg with lysate, load the CARDURAE-10 (C of 38.1Kg afterwards ₁₀the glycidyl ester of tertiary carboxylic acid).This mixture stirs and reacts with the amino group of the polyoxyethylene glycol-diamines condenses of the epoxide group and oxidation that make CARDURAE-10 for 1 hour at 93 DEG C.Measure solids content and add the water of extra 63.5Kg solids concn to be adjusted to the level of expectation.This product is loaded in multiple drum.

Final product has the amine nitrogen equivalent weight of the solids concn and 3281 (solid-based) of 63.7%.The high molecular weight peak of gel infiltration (size exclusion method) Chromatogram display at the peak molecular weight place at the lower molecular weight peak and 9268 (area of 31.4% may correspond to coupling material) at the peak molecular weight place of 4590 (areas of 64.2%) of product (polyoxyethylene glycol caliberator).Remaining area corresponds to the material of the molecular weight of hundreds of.The lower molecular weight peak be widened to especially corresponding to splitting of chain is not observed in lower molecular weight region.Total mixture has the number-average molecular weight of 3758 and the weight-average molecular weight of 6260.Based on GPC, the percentage ratio being present in the oligomeric amidoamine compound in amide amine composition is 31.4%.Polymolecularity, i.e. PD, relatively low and Mz is relatively low (Table II).

In the epoxy dispersion tensio-active agent of the low viscosity that the original surface promoting agent of this embodiment 4A embodiment 8 in for Table III, IV and V shows and low particle size, original position is formed effectively.But what also show is viscosity, epoxy equivalent weights and particle diameter increase significantly along with the time, provides the very limited shelf-lives being less than 1 year thus according to management.

Embodiment 4B is the product of embodiment 1 and the preparation embodiment of alkylation 1,3-propanediamine condenses and their aqueous solution.

4 mouthfuls of round-bottomed flasks of 1 liter are equipped with paddle agitator, thermopair, distillation delivery port (distillationtakeoff) and vacuum takeoff (vacuumtakeoff)/purging with nitrogen gas mouth.Product (after removing volatile matter) and following amine: the A of the embodiment 1B of Table I amount shown is loaded in this flask; N-oleoyl trimethylene diamine; B; N-(the tridecyl oxygen propyl group of branching) trimethylene diamine and C, N ((octyl group/decyl) oxygen propyl group) trimethylene diamine mixture.

215 DEG C are heated by temperature regulator with maximum heating speed with purging with nitrogen gas flask.Along with the carrying out of acid amides forming reactions, from reaction mixture, distill water outlet.Under the pressure of the reduction of 80-160Pa, 30 minutes (being 1 hour when mixture 3 and 5) is kept at this temperature afterwards when maintenance 215 DEG C 1 hour in this reaction mixture nitrogen at atmosheric pressure.Then, reaction mixture is cooled to about 90 DEG C and add water to prepare the aqueous solution.Measure the Brookfield viscosity at the percent solids of the aqueous solution and 25 DEG C.Also analyze this solution by gel permeation chromatography (GPC).The GPC chromatogram of often kind of solution all show three peaks, and it has the high molecular weight peak at the lower molecular weight peak at MW1000-1200 place, the intermediate molecular weight peak (close with the main peak position of starting raw material) at MW4300-4600 place and MW9300-9800 place.Calculate the area percent at each peak and be shown in lower Table I.

table I

Can see that from Table I condenses prepared by ether diamine B and C viscosity is in aqueous far below long chain hydrocarbon diamines A.

Embodiment 5 is the embodiments using the product of embodiment 2 to prepare amide amine original surface surfactant composition as starting raw material.

1200.0 grams are added from the carboxylated polyoxy oxyethane of the water-based of embodiment 2 in the resin flask being equipped with agitator, heating jacket, nitrogen nozzle and vacuum systems.By vacuum distilling at 91 DEG C from the product of embodiment 2 except anhydrating.Then by 154.8 grams of 2-methyl isophthalic acids, 5-pentane diamine (InvistaDytekA) adds in flask.Install condenser additional to flask to reflux to allow content.While the gentle bubbling of nitrogen, mixture be heated to 181 DEG C and mix 45 minutes under reflux at such a temperature.Application of vacuum and heating are to distill out excessive DytekA and water to form the reactant of acid amides amination.Under 181 DEG C of absolute pressures with 6.7KPa after 1 hour, the amide amine that carboxylated polyoxy oxyethane and DytekA are formed has the amine nitrogen equivalent weight of 2639.Then at 164 DEG C, use this batch materials of steam bubble of wet nitrogen amine nitrogen equivalent weight is brought up to 2865.After this batch materials is cooled to 110 DEG C, add deionized water solid is reduced to 70%.In this batch materials, 34 grams of CARDURAE-10 (C are added at 62 DEG C ₁₀the glycidyl ester of tertiary carboxylic acid).Allow after this batch materials mixes 2 hours at 55-62 DEG C, be diluted to the solid of 64.8% and allow it at room temperature to place to spend the night.

The amine nitrogen equivalent weight determination of water-based end-blocking amide amine polymkeric substance is 3079.For the preparation of epoxy dispersion as described in Example 11 after this original surface promoting agent, observe this dispersion and there is low viscosity.This original surface promoting agent also uses the epoxy dispersion preparing embodiment 9 together with the original surface promoting agent from embodiment 6, and compared with the embodiment 8 of " the prior art level " of contrast, this epoxy dispersion shows better shelf stabilities.

Embodiment 6 is the embodiments using embodiment 3 to prepare amide amine original surface surfactant composition as starting raw material.

1500.0 grams are added from the carboxylated polyoxy oxyethane of the water-based of the product of embodiment 3 in the resin flask being equipped with agitator, heating jacket, nitrogen nozzle and vacuum systems.By vacuum distilling at 91 DEG C from the product of embodiment 3 except anhydrating.Then by 95.3 grams of 2-methyl isophthalic acids, 5-pentane diamine (InvistaDytekA) adds in flask.Install condenser additional to flask to reflux to allow content.While the gentle bubbling of nitrogen, mixture be heated to 179 DEG C and under reflux conditions mix 45 minutes at such a temperature.Application of vacuum and heating are to distill out excessive DytekA and water to form the reaction reagent of acid amides amination.Under 181 DEG C of absolute pressures with 5.1KPa after 2.5 hours, the amide amine that carboxylated polyoxy oxyethane and DytekA are formed has the amine nitrogen equivalent weight of 2111.After the continous vacuum distillation of 3 hours, amine nitrogen equivalent weight is 4531.Then at 155 DEG C with wet this batch materials of nitrogen steam bubble amine nitrogen equivalent weight is brought up to 5013.After this batch materials is cooled to 110 DEG C, add deionized water solid is reduced to 70%.In this batch materials, 34 grams of CARDURAE-10 (C are added at 66 DEG C ₁₀the glycidyl ester of tertiary carboxylic acid).Allow after this batch materials mixes 2 hours at 55-62 DEG C, be diluted to the solid of 64.2% and allow it at room temperature to place to spend the night.

The amine nitrogen equivalent weight determination of water-based end-blocking amide amine polymkeric substance is 5333.For the preparation of epoxy dispersion as described in Example 12 after this original surface promoting agent, this dispersion has low pH value and outstanding epoxy content stability.This original surface promoting agent is also blended with the epoxy dispersion forming embodiment 9 with the dispersion from embodiment 5, and compared with the embodiment 8 of " the prior art level " of contrast, this epoxy dispersion shows the shelf stabilities of improvement.

Embodiment 7 is the blend preparation embodiments as the amide amine original surface surfactant composition preferred of the present invention of starting raw material of the product using embodiment 2 and embodiment 3.

2312.1 grams of carboxylated polyoxy oxyethane of the product water-based from embodiment 2 and 1890.0 grams of products from embodiment 3 are added in the stainless steel reactor being equipped with heating jacket, agitator, nitrogen nozzle and vacuum systems.By vacuum distilling under the absolute pressure of the highest 105 DEG C and 6.7KPa from blend except anhydrating.Then by 418.1 grams of 2-methyl isophthalic acids, 5-pentane diamine (InvistaDytekA) adds in this batch materials.Install condenser additional to flask to reflux to allow content.While the gentle bubbling of nitrogen, mixture be heated to 184 DEG C and under reflux conditions mix 45 minutes at such a temperature.Application of vacuum and heating are to distill out excessive DytekA and water to form the reactant of acid amides amination.Under 171-188 DEG C and 13.5 arrive the absolute pressure of 5.1KPa after 4 hours, the amide amine that carboxylated polyoxy oxyethane and DytekA are formed has the amine nitrogen equivalent weight of 3811.After this batch materials is cooled to 110 DEG C, add deionized water solid is reduced to 70%.Then at 66 DEG C, in this batch materials, 97.3 grams of CARDURAE-10 (C are added ₁₀the glycidyl ester of tertiary carboxylic acid).Allow after this batch materials mixes 2 hours at 70-83 DEG C, to be diluted to the solid of 64.3%.

The amine nitrogen equivalent weight determination of end-blocking amide amine polymkeric substance is 3750.The molecular weight dispersion DP of the blend of PEG4000 and PEG8000 as is expected, the common amidation blend of corresponding PEG acid of this embodiment 7 oxidation also has the molecular weight dispersion of 1.2895, but this compares substantially identical lower slightly with the molecular weight distribution of the associated blends of the acid amides amination original surface promoting agent of 6 with Table II illustrated embodiment 5.This amidation original surface promoting agent is also for the preparation of the epoxy dispersion of the preferred embodiment of the invention 9 altogether, and this dispersion has the viscosity lower than the embodiment of prior art level, less particle size and outstanding shelf stabilities.

Embodiment 8 is contrast aqueous dispersion embodiments, and it comprises the preparation of the epoxy dispersion prepared by the original surface promoting agent prepared according to the method described in embodiment 4.

936.9 grams of EPONResin828 and 285.1 gram dihydroxyphenyl propanes are added in the resin flask being equipped with heating jacket, agitator, nitrogen nozzle, vacuum systems and condenser.This batch materials is under agitation heated to 115 DEG C.Then in mixture, 1.0 grams of triphenylphosphines are added.This batch materials is under agitation heated to 132 DEG C and allows its heat release temperature rise to high to 190 DEG C.Then this batch materials keeps 45 minutes at 177 DEG C-190 DEG C.Afterwards this batch materials be cooled to 132 DEG C and add 99.3 grams of propylene glycol monomethyl ethers.This batch materials refluxes and is cooled to 105 DEG C.What then add 84.1 grams of embodiment 4A at atmosheric pressure has the high molecular content of 28.7%, the original surface promoting agent of the nitrogen of 3164 equivalent weights and the solid of 64.7%.This batch materials is allowed under agitation in 2.5 hours, to be cooled to 99 DEG C.Now fast 285.5 grams of deionized waters were joined in material in 5 minutes.This batch materials is under reduced pressure cooled to 77 DEG C, and now epoxy polymer and original surface promoting agent epoxide form water bag resin dispersion.

(this batch materials is cooled to 55 DEG C) after dispersion mixes extra 1.0 hours under the absolute pressure of 44.0KPa, average Sa diameter (surface-area) particle size is 0.723 micron and average Dv (volume) particle size is 1.105 microns.Now, make this batch materials turn back to barometric point and add 13.0 grams of acetone in this batch materials.This batch materials mix 15 minutes at 55 DEG C and the polypropylene glycol solution adding the Witco 1298 Soft Acid of 1.26 gram 50% with control ph close to neutral.This batch materials mixes extra 15 minutes and in 10 minutes, adds 26.0 grams of HELOXYModifier8 afterwards.This batch materials mixes 20 minutes and allows its cool overnight afterwards.This batch materials was under agitation heated to 52 DEG C by the next morning in 1.0 hours.In 2 hours, dilute this batch materials with deionized water, period allowable temperature be cooled to 48 DEG C.

This batch materials is mixed extra 20 minutes and is filtered by 80 order filter bags afterwards.Sample dilute further be 55.9%, 54.2% and 51.8% non-volatile substance.Measure the BrookfieldRVDVI of this batch materials on the same day in dilution, be respectively 16,740cP, 7,040cP and 2,600cP, measure with 20rmp at 25 DEG C with spindle 5.Under corresponding % solid, initial viscosity (at 49 DEG C after 1 day/after 2 days, balance to allow exhaust and pH value at 25 DEG C) is 15,560cP, 5,900cP and 1,620cP.The particle size of this final epoxy dispersion is Sa0.743 and Dv0.942 micron.The epoxide equivalent weight of resin content is 504.At 49 DEG C, after 1 day, add that the pH value of this batch materials after 1 day at 25 DEG C is 8.60.As shown in Table III, the epoxy dispersion that prepared by this use embodiment 4, standard original surface promoting agent has low particle size, medium initial viscosity and relative high pH value.This high pH value facilitates the speed of relatively fast viscosity and epoxy equivalent weights increase as shown in Table III.Therefore the shelf-lives of prior art is restricted to and is less than 1 year by the increase of viscosity and epoxy equivalent weights.

The structure of the tensio-active agent of the prior art level of embodiment 8 is following structure, and wherein n is 1.2.

Embodiment 9A is the preparation embodiment of the epoxy dispersion prepared by the blend of the corresponding original surface promoting agent of the embodiment 5 of 55:45 ratio and embodiment 6.

933.3 grams of EPONResin828 and 289.5 gram dihydroxyphenyl propanes are added in the resin flask being equipped with heating jacket, agitator, nitrogen nozzle, vacuum systems and condenser.This batch materials is under agitation heated to 105 DEG C.Then in mixture, 1.0 grams of triphenylphosphines are added.This batch materials is under agitation heated to 132 DEG C and allows its heat release temperature rise to high to 190 DEG C.Then this batch materials keeps 45 minutes at 177 DEG C-190 DEG C.Afterwards this batch materials be cooled to 136 DEG C and add 99.3 grams of propylene glycol monomethyl ethers.This batch materials refluxes and is cooled to 105 DEG C.Then the material of 47.0 grams of embodiments 5 and 38.4 grams of embodiments 6 (amounting to 85.4g) is added at atmosheric pressure.This batch materials is allowed under agitation in 2.0 hours, to be cooled to 99 DEG C.Now, fast 284.6 grams of deionized waters were joined in this batch materials in 5 minutes.This batch materials is under reduced pressure cooled to 77 DEG C, and now epoxy polymer and original surface promoting agent epoxide form water bag resin dispersion.

(this batch materials is cooled to 55 DEG C) after dispersion mixes extra 2.5 hours under the absolute pressure of 44.0KPa, average Sa diameter (surface-area) particle size is 0.875 micron and average Dv (volume) particle size is 1.345 microns.Now, make this batch materials turn back to barometric point and in material, add 13.0 grams of acetone.This batch materials mix 5 minutes at 55 DEG C and the polypropylene glycol solution adding the Witco 1298 Soft Acid of 1.26 gram 50% with control ph close to neutral.This batch materials mixes extra 10 minutes and in 10 minutes, adds 26.0 grams of HELOXYModifier8 afterwards.This batch materials mixes 20 minutes and allows its cool overnight afterwards.This batch materials was under agitation heated to 54 DEG C by the next morning in 1.0 hours.In 2 hours, dilute this batch materials with deionized water, period allowable temperature be cooled to 50 DEG C.

This batch materials is mixed extra 20 minutes and is filtered by 80 order filter bags afterwards.Sample dilute further be 55.7%, 54.5% and 52.1% non-volatile substance.Its fresh viscosity at 25 DEG C (as measured in embodiment 8) is respectively 15,160cP, 6,160cP and 2,020cP.The initial viscosity (at 49 DEG C after 1 day/at 25 DEG C after 2 days) measured is respectively 15,960cP, 5,100cP and Isosorbide-5-Nitrae 80cP.The particle size of this final epoxy dispersion is Sa0.862 and Dv1.428 micron.The epoxide equivalent weight of resin content is 506.At 49 DEG C, after 1 day, the pH value of this batch materials adds that the pH value at 25 DEG C after 2 days is 8.18.As shown in Table III, the pH value of this dispersion causes the speed ratio standard scores prose style free from parallelism embodiment 8 of viscosity and epoxy equivalent weights increase higher.As shown in Table III, this dispersion also has than both embodiments 11 and 12 all better shelf stabilities.

Embodiment 9B is the preparation embodiment of the epoxy dispersion prepared by the blend of the embodiment 5 of 85:15 ratio and the respective original surface promoting agent of embodiment 6.This epoxy dispersion is prepared by the following process identical with embodiment 9A, except the weight ratio of the active original surface promoting agent by embodiment 5 and embodiment 6 is adjusted to 85:15 respectively.

Embodiment 9C is the preparation embodiment of the epoxy dispersion prepared by the blend of the embodiment 5 of 70:30 ratio and the respective original surface promoting agent of embodiment 6.This epoxy dispersion is prepared by the following process identical with embodiment 9A, except the weight ratio of the active original surface promoting agent by embodiment 5 and embodiment 6 is adjusted to 70:30 respectively.

Embodiment 10 is by the preparation embodiment of the epoxy dispersion prepared according to the original surface promoting agent product of embodiments of the invention 7.

936.8 grams of EPONResin828,285.6 grams of dihydroxyphenyl propanes and 1.0 grams of triphenylphosphines are added in the resin flask being equipped with heating jacket, agitator, nitrogen nozzle, vacuum systems and condenser.This batch materials is under agitation heated to 105 DEG C.Then in mixture, 1.0 grams of triphenylphosphines are added.Its pressure is made to be reduced to the absolute pressure of 20.3KPa with purging with nitrogen gas flask.This batch materials is under agitation heated to 130 DEG C and allows its heat release temperature rise to high to 194 DEG C.Allow at atmosheric pressure this batch materials to be cooled to 176 DEG C in 1.5 hours.This batch materials is cooled to 151 DEG C and adds 99.3 grams of propylene glycol monomethyl ethers.Under reduced pressure make this batch materials reflux cooling to 99 DEG C.Then the material of 84.6 grams of embodiments 7 is added at atmosheric pressure.This batch materials is allowed under agitation in 1.8 hours, to be cooled to 96 DEG C.Now in 2 minutes, 285.1 grams of deionized waters are joined in this batch materials.This batch materials is under reduced pressure cooled to 75 DEG C, and now, epoxy polymer and original surface promoting agent epoxide form water bag resin dispersion.

(this batch materials is cooled to 57 DEG C) after dispersion mixes extra 1.5 hours under the absolute pressure of 37.3KPa, average Sa diameter (surface-area) particle size is 0.869 micron and average Dv (volume) particle size is 1.274 microns.Now, make this batch materials turn back to barometric point and in material, add 13.0 grams of acetone.This batch materials mix 20 minutes at 57 DEG C and the polypropylene glycol solution adding the Witco 1298 Soft Acid of 1.26 gram 50% with control ph close to neutral.This batch materials mixes extra 20 minutes and in 10 minutes, adds 26.0 grams of HELOXYModifier8 afterwards.This batch materials mixes 1 hour and allows it to be cooled to 22 DEG C to spend the night afterwards.This batch materials was under agitation heated to 53 DEG C by the next morning in 1.25 hours.

Then in 2 hours by this batch materials dilution be 52.2% solid, period allowable temperature be cooled to 32 DEG C.This batch materials is mixed extra 20 minutes and is filtered by 80 order filter bags afterwards.The particle size of this final epoxy dispersion is Sa0.680 and Dv1.013 micron.Material viscosity fresh at 25 DEG C is 1,200cP.The epoxide equivalent weight of resin content is 513.Add after 1 day at 49 DEG C the pH value of this batch materials after 3 days at 25 DEG C be 7.47 and according to embodiment 8 be described at 25 DEG C measure viscosity be 1,060cP.As shown in Table IV, compared with the embodiment 8 of " prior art level " and every other embodiment, this dispersion has minimum initial viscosity distribution.This dispersion is also minimum and under lower pH, have outstanding epoxy equivalent weights stability (see Table III) in particle size.

It is believed that the tensio-active agent of embodiment 10 has following structure:

Wherein R is the alkyl chain of C9 branching, and n is 0,1 or 2, and obtains the mean value of x=131 by 55 parts of X=81+45 part X=192.

Embodiment 11 is preparation comparative examples of epoxy dispersion prepared by the original surface promoting agent prepared by the method described according to embodiment 5.

933.7 grams of EPONResin828 and 288.2 gram dihydroxyphenyl propanes are added in the resin flask being equipped with heating jacket, agitator, nitrogen nozzle, vacuum systems and condenser.This batch materials is under agitation heated to 110 DEG C.Then in mixture, 1.0 grams of triphenylphosphines are added.This batch materials is under agitation heated to 132 DEG C and allows its heat release temperature rise to high to 190 DEG C.Then this batch materials keeps 45 minutes at 177 DEG C-190 DEG C.Afterwards this batch materials be cooled to 133 DEG C and add 99.3 grams of propylene glycol monomethyl ethers.This batch materials refluxes and is cooled to 105 DEG C.Then add 84.0 grams of materials prepared by the method for embodiment 5 at atmosheric pressure, but this material has the high molecular weight peak content of 30.8%, the titratable nitrogen of 2863 equivalent weights and the solid of 64.8%.This batch materials is allowed under agitation in 2.25 hours, to be cooled to 98 DEG C.Now, fast 285.5 grams of deionized waters were joined in material in 10 minutes.This batch materials is under reduced pressure cooled to 74 DEG C, and now, epoxy polymer and original surface promoting agent epoxide form water bag resin dispersion.

(this batch materials is cooled to 55 DEG C) after dispersion mixes extra 2.0 hours under the absolute pressure of 44.0KPa, average Sa diameter (surface-area) particle size is 0.875 micron and average Dv (volume) particle size is 1.324 microns.Now, make this batch materials turn back to barometric point and in material, add 13.0 grams of acetone.This batch materials mix 20 minutes at 54 DEG C and the polypropylene glycol solution adding the Witco 1298 Soft Acid of 1.3 gram 50% with control ph.This batch materials mixes extra 20 minutes and in 10 minutes, adds 26.0 grams of HELOXYModifier8 afterwards.This batch materials mixes 35 minutes and allows it under not mixing, be cooled to 22 DEG C afterwards and spends the night at 54 DEG C.This batch materials under agitation slowly was heated to 53 DEG C by the next morning in 1 hour.In 1.5 hours, dilute this batch materials with deionized water, period allowable temperature be cooled to 50 DEG C.

This batch materials is mixed extra 20 minutes and is filtered by 80 order filter bags afterwards.Sample dilute further be 55.9%, 53.8% and 52.0% non-volatile substance.Measure the BrookfieldRVDVI of this batch materials on the same day in dilution, be respectively 27,600cP, 9,560cP and 1,700cP, measure with 20rmp at 25 DEG C with spindle 5 (or using spindle 6 for higher than 20,000cP).Under corresponding % solid, initial viscosity (adding after 1 day at 49 DEG C at 25 DEG C after 2 days to allow exhaust and pH value to balance) is 22,200cP, 5,980cP and 920cP.The particle size of this final epoxy dispersion is Sa0.835 and Dv1.301 micron.The epoxide equivalent weight of resin content is 518.At 49 DEG C, after 1 day, add that the pH value of this batch materials after 1 day at 25 DEG C is 8.79.This dispersion has low initial viscosity, but both viscosity and epoxy equivalent weights are all unstable and pH value is high.As shown in Table IV, this dispersion at 25 DEG C between the shelf lives its viscosity increase faster than embodiment 8.

Embodiment 12 is preparation comparative examples of epoxy dispersion prepared by the original surface promoting agent prepared by the method described according to embodiment 6.

933.5 grams of EPONResin828 and 288.9 gram dihydroxyphenyl propanes are added in the resin flask being equipped with heating jacket, agitator, nitrogen nozzle, vacuum systems and condenser.This batch materials is under agitation heated to 104 DEG C.Then in mixture, 1.0 grams of triphenylphosphines are added.This batch materials is under agitation heated to 132 DEG C and allows its heat release temperature rise to high to 190 DEG C.Then this batch materials keeps 55 minutes at 177 DEG C-190 DEG C.Afterwards this batch materials be cooled to 141 DEG C and add 99.3 grams of propylene glycol monomethyl ethers.This batch materials refluxes and is cooled to 109 DEG C.Then add 84.7 grams of materials prepared by the method for embodiment 6 at atmosheric pressure, but this material has the high molecular weight peak content of 27.14%, the titratable nitrogen of 2863 equivalent weights and the solid of 64.2%.This batch materials is allowed under agitation in 2.0 hours, to be cooled to 98 DEG C.Now fast 285.0 grams of deionized waters were joined in material in 10 minutes.This batch materials is under reduced pressure cooled to 74 DEG C, and now epoxy polymer and original surface promoting agent epoxide form resin in water dispersion.

(this batch materials is cooled to 54 DEG C) after dispersion mixes extra 1.0 hours under the absolute pressure of 33.8KPa, average Sa diameter (surface-area) particle size is 0.836 micron and average Dv (volume) particle size is 1.329 microns.Now, make this batch materials turn back to barometric point and in material, add 13.0 grams of acetone.This batch materials mix 20 minutes at 54 DEG C and the polypropylene glycol solution adding the Witco 1298 Soft Acid of 1.3 gram 50% with control ph close to neutral.This batch materials mixes extra 20 minutes and in 10 minutes, adds 26.0 grams of HELOXYModifier8 afterwards.This batch materials mixes 1 hour.In 1.5 hours, dilute this batch materials with deionized water, period allowable temperature be cooled to 50 DEG C.

This batch materials is mixed extra 20 minutes and is filtered by 80 order filter bags afterwards.Sample dilute further be 55.8%, 53.9% and 52.0% non-volatile substance.At the BrookfieldRVDVI measuring this batch materials on the same day of dilution, be respectively 8,060cP, 3,660cP and 1,680cP, measure with 20rmp at 25 DEG C with spindle 5.Under corresponding % solid, initial viscosity (add after 1 day at 25 DEG C after 2 days at 49 DEG C, balance to allow exhaust and pH value) is 15,920cP, 3,360cP and Isosorbide-5-Nitrae 60cP.The particle size of this final epoxy dispersion is Sa0.873 and Dv1.288 micron.The epoxide equivalent weight of resin content is 513.At 49 DEG C, after 1 day, add that the pH value of this batch materials after 1 day at 25 DEG C is 7.29.Although the pH value of this dispersion and epoxy equivalent weights stability are preferred, the comparatively large and initial viscosity higher than the initial viscosity of preferred embodiment 10 (as shown in Table III and IV) of its particle size.

The embodiment of embodiment 13 to be blend co-oxidation being respectively the preferred polyoxyethylene glycol (PEG) of 4000 and 8000 number-average molecular weights of 55 to 45 ratios be carboxylic acid functionalized tensio-active agent.

Being respectively of 55 to 45 ratios (the PEG4000 glycol of 20.0 pounds and the PEG8000 glycol of 16.36 pounds) 4000 is together oxidized to corresponding dicarboxylic acid according to the method identical with embodiment 3 (also according to the method that U.S. patent 6956086B2 embodiment 1 is summarized) as the aqueous solution with preferred polyoxyethylene glycol (PEG) blend of 8000 number-average molecular weights.Repeat the method and blended two kinds of products.The PEG acid obtained in water, be adjusted to the concentration of 59.4% and the weight in average of every acid of PEG carboxylicesters is measured as 3629.

Embodiment 14 uses embodiment 13 as the preparation embodiment of the amide amine original surface surfactant composition of starting raw material.The reactor content of embodiment 13 is converted into amide amine original surface promoting agent by the method identical with embodiment 5.The original surface promoting agent obtained has the amine nitrogen equivalent weight of 4065 and the Non-volatile content of 63.0%.

Embodiment 15 is that the method described by embodiment 8 uses the original surface promoting agent of embodiment 14 to prepare the embodiment of epoxy dispersion.

The epoxy dispersion obtained by the original surface promoting agent from embodiment 14 has the typical average micron diameter particle size distribution of Dv0.870, Sa0.623, Dn0.633 and Dw0.814.The epoxy equivalent weights of polymkeric substance of dispersion is the viscosity under 507,52.2%NV is 1,220cP.This epoxy dispersion uses to prepare the high-performance priming paint that embodiment 17 describes together with the amine hardener of embodiment 16.

Embodiment 16 is the embodiments using the original surface promoting agent from embodiment 14 to prepare amine hardener dispersion.

With with U.S. patent 6,277, the similar mode of process that 928 embodiments 1 describe, make the original surface promoting agent of embodiment 14 and excessive EPON1001X75 solution with 5.5 to 94.5 ratio react.Follow-up and the relative every equivalent epoxide of this epoxy original surface promoting agent adducts is that the Triethylenetetramine (TETA) (TETA) of 3 moles reacts.After having reacted, the volatile matter comprising 2 molar excess TETA is removed by vacuum distilling.Then relatively every unreacted primary amine of equivalent adds 1 mole of monocycle oxygen Heloxy62.Then this amine-functionalized adduct polymerization thing is dispersed in water to obtain the white dispersion of the average micron-scale diameter with Dv0.516 and Sa0.423.The content of the non-volatile substance of this dispersion is 51.6% and the amine value of nv polymer is 257.This amine-functionalized polymeric dispersions is used for combining to prepare the high-performance priming paint described in embodiment 18 with the epoxy dispersion of embodiment 15.

The MomentiveSF1700 of the epoxide of embodiment 15 and the amine dispersion of embodiment 16 paints performance and comprises the HoursThruDry of 1.25 hours, the H pencil SF1700(7DayPencilSF1700ofH of 7 days) and initial time and the SF1700KU viscosity checked for 3 hours be respectively 71 and 68.By contrast, derived from embodiment 4 original surface promoting agent be purchased standard epoxy compound and amine dispersion comprise the HoursThruDrySF1700 of 1.75 hours, the H pencil SF1700 of 7 days and initial time and the SF1700KU viscosity of check in 3 hours be respectively 54 and 78.

Embodiment 17 is the embodiments using the original surface promoting agent from embodiment 7 to prepare amine hardener dispersion.

With with U.S. patent 6,277, the similar mode of process that 928 embodiments 1 describe, make the original surface promoting agent of embodiment 7 and excessive EPON1001X75 solution with 5.5 to 94.5 ratio react.Follow-up and the relative every equivalent epoxide of this epoxy original surface promoting agent adducts is that the Triethylenetetramine (TETA) (TETA) of 3 moles reacts.After having reacted, the volatile matter comprising 2 molar excess TETA is removed by vacuum distilling.Then relatively every unreacted primary amine of equivalent adds 1 mole of monocycle oxygen Heloxy62.Then this amine-functionalized adduct polymerization thing is dispersed in water to obtain the white dispersion of the average micron-scale diameter with Dv0.331 and Sa0.219.The content of the non-volatile substance of this dispersion is 51.2% and the amine value of nv polymer is 242.This amine-functionalized polymeric dispersions is used for combining to prepare the high-performance priming paint described in embodiment 18 with the epoxy dispersion of embodiment 15.

The MomentiveSF1700 of the epoxide of embodiment 15 and the amine dispersion of embodiment 17 paint performance comprise the HoursThruDry of 1.5 hours, the F+ pencil SF1700 of 7 days and initial time and the SF1700KU viscosity checked for 3 hours be respectively 68 and 73.By contrast, derived from embodiment 4 original surface promoting agent be purchased standard epoxy compound and amine dispersion comprise the HoursThruDrySF1700 of 1.75 hours, the F+ pencil SF1700 of 7 days and initial time and the SF1700KU viscosity of check in 3 hours be respectively 54 and 78.

Embodiment 18 is by the embodiment of the dispersion priming paint using the above amide amine original surface promoting agent defined by following MomentivepublishedStartingPointFormulation1700 to prepare.

Make the epoxy resin dispersion that describes in the embodiment of the present invention 15 of 300.0lbs (33.33 gallons) and the PPH propylene glycol phenyl ether (from DowChemical) of 26.0lbs (2.95 gallons), 3.0lbs (0.35 gallon) 2526Defoamer (from CIBASpecialtyCompany), 100.0lbs's (3.1 gallons) the 10ES of R-960 pigment (from DuPont), 100.0lbs (4.12 gallons) the Sparmite of (from NYCOMinerals, Inc.), 67.0lbs (1.83 gallons) ^tMa barite (from ElementisPigmentsInc.), 94.7lbs's (3.98 gallons) the wet lapping mica of SW-111 (from HALOXPigments), 7.0lbs (0.3 gallon), 325 orders (from FranklinIndustrialMinerals) mixing.High speed dispersion process is carried out to provide the texture structure of 5-6HegmanScale to this mixture.Reduce mixing velocity and add the CoatOSil of EPI-REZResin6520-WH-53 (from MomentiveSpecialtyChemicals), the 8.6lbs (0.98 gallon) of 107.5lbs (11.94 gallons) afterwards ^tMthe water of 1770Silane (from MomentivePerformanceProducts) and 142.9 (7.12 gallons).Now, mixture comprises the composition of 959.7lbs (80.0 gallons).The solidifying agent dispersion (from MomentiveSpecialtyChemicals) as embodiments described herein 17 of 180lbs (19.78 gallons) and Raybo60 flash of light rust-preventive agent (from Raybo) of 2lbs (0.22 gallon) is added in this mixture.Said composition is modulated to the stoichiometric ratio (epoxy group(ing): amine equivalent) of 1:1.

Embodiment 19 uses the original surface promoting agent of embodiment 7 for the preparation of the embodiment of the epoxy dispersion of fiber sizing material.

From embodiment 7 original surface promoting agent can also for the preparation of for comprise minimizing or the moisture epoxy dispersion of the fiber sizing material that do not comprise volatile solvent or tackiness agent.99.7 grams of liquid-state epoxy resins are added, EPON828, the original surface promoting agent of 102.5 grams of water-based embodiments 7 and 200.0 grams of deionized waters in the resin containers of 3 liters.To flask install agitator and water-cooled condenser additional in case when mixing heating material to 180 °F of periods, it comprises water vapour.

Allow this batch materials to react 1 hour at this temperature and add 1.6 grams of Witco 1298 Soft Acids afterwards.Then dilute this batch materials with 200.0 grams of water further, allow it to be cooled to 160 °F and in 30 minutes, add 1141.8 grams of extra EPON828 afterwards under good agitation.Allow under agitation in 2 hours this batch materials be cooled to 125 °F, and add 140.0 grams of water afterwards, and then add 0.7 gram of Rhodaline640 defoamer.This batch materials mixes 1.5 hours and adds 340.3 grams of extra water with 11.0 grams of OptifloH600VF afterwards and is diluted to 54.2%NV under 125-132 °F.Allow this batch materials to be cooled to slowly, after 25 DEG C, not stir in 16 hours, the viscosity measured under 20rpm by Brookfield spindle 5 is 1,240cP.Particle size is Dv0.71, and the epoxy equivalent weights of the polymkeric substance of dispersion is 197.2 and its pH value is 6.9.

Embodiment 20 is the embodiments using embodiment 13 and isodecyl oxygen propyl group-1,3-diaminopropanes to prepare amide amine original surface surfactant composition as starting raw material.

2195.1 grams of water-baseds from embodiment 13, carboxylated polyoxygenated oxyethane is added in the 3 liters of 4 mouthfuls of flasks being equipped with agitator, heating jacket, nitrogen nozzle and vacuum systems.By vacuum distilling at 91 DEG C from the product of embodiment 13 except anhydrating.Then 118.2 grams of isodecyl oxygen propyl group-1,3-diaminopropanes are added in flask.215 DEG C are heated by the maximum heating speed that temperature regulator sets with purging with nitrogen gas flask.Along with the carrying out of acid amides forming reactions, from reaction mixture, distill water outlet.Reaction mixture in nitrogen at 165 DEG C keep 3 hours with xylenes and catch amidation collection water.Under reduced pressure under strong nitrogen bubble, remove removal xylene and remaining water.Then amide amine product is cooled to 90 DEG C and dilute with water is the solid of 65.0%.The amine nitrogen equivalent weight determination of the amide amine polymkeric substance (solid-based) of water-based end-blocking is 3610.This original surface promoting agent is for the preparation of the low viscosity epoxy dispersion of embodiment 21.

Embodiment 21 is that the method described by embodiment 10 uses the original surface promoting agent of embodiment 20 to prepare the embodiment of epoxy dispersion.

Prepare dispersion by the process identical with embodiment 10, but use the original surface promoting agent of embodiment 20.The epoxy dispersion using the original surface promoting agent of embodiment 20 to obtain has the typical average micron diameter particle size distribution of Dv1.39, Dn0.84 and Dw1.14.The epoxy equivalent weights of the polymkeric substance of this dispersion be the viscosity under 529,53.75%NV be 360cps and at 25 DEG C after 24 hours the pH value of dispersion be 8.38.

Lower Table II shows the molecular weight of the amide amine original surface promoting agent of the comparative example between the method and composition of prior art and composition described in the invention and method.

table II

See from Table II, the polymolecularity compared from the original surface promoting agent of independent PEG compound from the acid amides amination of PEG blend or the polymolecularity (PD) of common amidation original surface promoting agent is high.

Lower Table III shows composition that the composition of prior art, dispersion 1,2 and 3 and the present invention describe, dispersion 4, comparative example between 5 and 6.The particle size of epoxy dispersion is less, and pH value is lower, and the viscosity of epoxy dispersion 5 and 6 is lower and shelf-lives is longer, and it is most preferably for commercial applications.

table III

Final pH at room temperature measures the pH value of two (or more than 6,000cP) viscosity at this time point.

Lower Table IV provides viscosity stability and the contrast compared with long shelf-life at 25 DEG C.As follows, as compared to the epoxy dispersion (embodiment 8,11 and 12) of prior art, the epoxy dispersion prepared by blend (embodiment 9 and 10) provides viscosity results that is equivalent or that improve.Following viscosity measurement is in centipoise (cP or cps).

table IV

The Brookfield viscosity of 20rmp at * 25 DEG C, spindle 5

Lower Table V provides the contrast of epoxy equivalent weights stability after 15 months at 25 DEG C between composition and the composition of prior art described according to the present invention in detail.Most preferred embodiment 10 of the present invention and preferred embodiment 9 have epoxy equivalent weights stability more significantly improved than the comparative examples 8 and 11 of prior art level.

table V

The contrast of what the figure shown in lower Table VI and Fig. 1 was detailed provide between composition as described in the present invention and the composition of prior art particle size stability.Table VI illustrates the prior art developmental level contrast of the particle size stability of embodiment 9 and 10 having thus described the invention higher than display in embodiment 8.Fig. 1 shows the particle size stability figure of epoxy dispersion epoxy dispersion at 25 DEG C that contrast is formed according to the embodiment 11 and 12 of embodiment of the present invention 9A, 9B and 9C and contrast prior art.

table VI

Dv changes	Comparative examples 8	Blend embodiment 9	Amidation embodiment 10 altogether
				Δ	0.613	0.420	0.312
Initial Dv	0.942	1.248	1.073
				Dv10 month	1.555	1.668	1.385

Although the present invention is described with reference to special embodiment and illustrates, to those those of ordinary skill in the art it is evident that the present invention be also suitable for change and without the need to here illustrating.

Claims

1. an amide amine composition, it comprises the reaction product of following material:

The polyoxyalkylene composition of the acid blocked of the polyoxyalkylene polyol compound of two or more acid blocked, wherein the polyoxyalkylene composition of acid blocked has 1.1 or more much higher dispersivenesses, and the polyoxyalkylene polyol compound of two or more acid blocked has the carboxyl end groups be oxidized by hydroxyl end groups of 50% to 100%; And

Diamine compound, it comprises the second amine substituting group of the substituent first amine substituting group of primary amine and primary amine substituting group or Secondary amine substituents, and wherein this reaction product comprises the amide amine compound with following formula:

Wherein R ₁and R ₂in each be hydrogen atom or the substituting group of group being selected from the branching with 1 to 21 carbon atoms or linear aliphatic, alicyclic, aromatic substituents and their combination, and R ₁and R ₂in at least one be hydrogen atom, R ₃it is divalence hydrocarbon substituent, it is selected from the group of the branching with 2 to 18 carbon atoms or linear aliphatic, alicyclic, aromatic substituents and their combination, n is the mean number of 18 to 500, m is 1 to 11, X is hydrogen atom or the substituting group being selected from the group be made up of methyl substituents, ethyl substituent, hydroxymethyl substituents and their combination, and Y is the substituting group of hydrogen atom or the group being selected from methyl substituents, ethyl substituent, hydroxymethyl substituents and their combination composition.

2. the composition of claim 1, wherein amide amine compound comprises the amine value of 8 to 30.

3. the composition of claim 1, wherein diamine compound comprises two primary amine substituting groups, and diamines has following formula:

H ₂N-R ₃-NH ₂,

Wherein R ₃be divalence hydrocarbon substituent, it is selected from the group of the branching with 2 to 18 carbon atoms or linear aliphatic, alicyclic, aromatic substituents and their combination.

4. the composition of claim 3, wherein provides diamine compound with the carboxyl end groups stoichiometric excess of the polyoxyalkylene composition of the relative acid blocked of amine substituting group.

5. the composition of claim 3, wherein reaction product comprises mono-epoxy compound further.

6. the composition of claim 1, wherein diamine compound comprises primary amine substituting group and Secondary amine substituents, and diamines has following formula:

R ₁-HN-R ₃-NH ₂

Wherein R ₁branching or linear aliphatic, the alicyclic or aromatic substituents with 1 to 21 carbon atoms, and R ₃be divalence hydrocarbon substituent, it is selected from the group of the branching with 2 to 18 carbon atoms or linear aliphatic, alicyclic, aromatic substituents and their combination.

7. the composition of claim 6, wherein R ₁substituting group comprises the end group of group being selected from methyl group, oh group and their combination further, and R ₃substituting group comprises the end group of group being selected from methyl group, oh group and their combination further.

8. the composition of claim 7, wherein R ₁substituting group, R ₃substituting group or the two on substituent main chain, comprise one or more non-reacted oxygen or nitrogen-atoms all further.

9. the composition of claim 1, each in two or more polyoxyalkylene polyol compounds wherein said is reacted with diamine compound all individually and merges afterwards to form amide amine composition.

10., for the formation of a method for amide amine composition, it comprises:

The polyoxyalkylene composition of the acid blocked of the polyoxyalkylene polyol compound of two or more acid blocked is provided, wherein the polyoxyalkylene composition of acid blocked there are 1.1 or more much higher dispersivenesses and the polyoxyalkylene polyol compound of two or more acid blocked described have 50% to 100% the carboxyl end groups be oxidized by hydroxyl end groups;

There is provided and comprise the substituent first amine substituting group of primary amine, and the substituent diamine compound of the second amine of primary amine substituting group or Secondary amine substituents; And

The polyoxyalkylene composition of acid blocked and diamine compound are reacted with forming reactions product, and wherein reaction product comprises the amide amine compound with following formula:

Wherein R ₁and R ₂in each be hydrogen atom or the substituting group of group being selected from the branching with 1 to 21 carbon atoms or linear aliphatic, alicyclic, aromatic substituents and their combination, and R ₁and R ₂in at least one be hydrogen atom, R ₃it is divalence hydrocarbon substituent, it is selected from the group of the branching with 2 to 18 carbon atoms or linear aliphatic, alicyclic, aromatic substituents and their combination, n is the mean number of 18 to 500, m is 1 to 11, X is hydrogen atom or the substituting group being selected from the group be made up of methyl substituents, ethyl substituent, hydroxymethyl substituents and their combination, and Y is hydrogen atom or the substituting group of group being selected from methyl substituents, ethyl substituent, hydroxymethyl substituents and their combination.

The method of 11. claims 10, wherein amide amine compound comprises the amine value of 8 to 30.

The method of 12. claims 10, wherein provides diamine compound to comprise and provides and have two primary amine substituting groups and the diamine compound with following formula:

H ₂N-R ₃-NH ₂,

The method of 13. claims 12, wherein provides diamine compound to comprise and provides diamine compound with the amine substituting group of the carboxylic end group stoichiometric excess of the polyoxyalkylene composition of relative acid blocked.

The method of 14. claims 12, it comprises further makes described reaction product and the composition react containing single epoxy group(ing).

The method of 15. claims 10, wherein provide diamine compound to comprise the diamine compound providing and have primary amine substituting group and Secondary amine substituents, and this diamines has following formula:

R ₁-HN-R ₃-NH ₂,

The method of 16. claims 15, wherein R ₁substituting group comprises the end group of group being selected from methyl group, oh group and their combination further, and R ₃substituting group comprises the end group of group being selected from methyl group, oh group and their combination further.

The method of 17. claims 16, wherein R ₁substituting group, R ₃substituting group or the two in substituent main chain, comprise one or more non-reacted oxygen or nitrogen-atoms all further.

The method of 18. claims 10, each in two or more polyoxyalkylene polyol compounds wherein said all reacts separately to form amide amine compound with diamine compound, and comprises further amide amine compound is mixed mutually.

The method of 19. claims 10, it comprises further makes described reaction product and epoxy composite react to form epoxy-functional amide amine composition.

The method of 20. claims 19, wherein epoxy composite comprises bicyclic oxygen component.

The method of 21. claims 20, wherein bicyclic oxygen component comprises the mixture of diepoxy resin or diepoxy resin and phenolic compound.

The method of 22. claims 19, wherein epoxy composite comprises at least one and has the epoxy resin that per molecule is greater than the epoxide group functionality of 0.8.

The method of 23. claims 19, wherein epoxy composite comprises ethoxyl substitution relative to amine groups stoichiometric excess and water, and this epoxy-functional amide amine composition comprises aqueous epoxy resins dispersion.

The method of 24. claims 23, wherein epoxy-functional amide amine composition comprises the dispersion of 1wt.% to 20wt.%.

The method of 25. claims 19, wherein epoxy-functional amide amine composition comprises the epoxy-functional tensio-active agent with following formula:

Wherein m is 1 to 11, n be 1 to 3, q is 0 to 8, p is 18 to 500, X is hydrogen atom, methyl substituents, ethyl substituent, hydroxymethyl substituents or their combination, and each Y is hydrogen atom, methyl substituents, ethyl substituent, hydroxymethyl substituents or their combination, and R ₁₇can be alkyl group, aromatic yl group, carboxyl groups and their combination.

The method of 26. claims 19, it comprises further makes epoxy-functional amide amine composition and polyamine compounds react.